[ { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/qkc4v-vzc32", "eprint_status": "archive", "datestamp": "2023-12-13 19:30:02", "lastmod": "2023-12-13 19:30:03", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Wang-Zhuo-Yan", "name": { "family": "Wang", "given": "Zhuo-Yan" } }, { "id": "Freas-Dylan-J", "name": { "family": "Freas", "given": "Dylan J." }, "orcid": "0000-0003-0611-7907" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Phosphine Catalysis of the Fluorination of Unactivated Tertiary Alkyl Chlorides under Mild and Convenient Conditions", "ispublished": "pub", "full_text_status": "public", "keywords": "Colloid and Surface Chemistry; Biochemistry; General Chemistry; Catalysis", "note": "
\u00a9 2023 American Chemical Society.
\n\nThis study is dedicated to the memory of Prof. Jeffery A. Byers (Boston College). We thank Dr. Mona Shahgholi (Mass Spectrometry Facility), Dr. Michael K. Takase (X-ray Crystallography Facility) Dr. David G. Vander Velde (NMR Facility), Dr. Scott C. Virgil (Center for Catalysis and Chemical Synthesis), Carlos E. Del Angel Aguilar, Jay P. Barbor, Hyungdo Cho, Dr. Hien Do, Xiaoyu Tong, Dr. Zhaobin Wang, and Dr. Feng Zhong for assistance and for helpful discussions. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences; grant R35-GM145315), the Beckman Institute of the California Institute of Technology, the Gordon and Betty Moore Foundation (grant to the California Institute of Technology), and the Dow Next-Generation Educator Fund (grant to the California Institute of Technology).
\n\nThe authors declare no competing financial interest.
\n\nCCDC 2294879 and 2294881 contain the supplementary crystallographic data for this paper.
", "abstract": "Due to the significance of organofluorine compounds in disciplines ranging from medicine to agriculture to materials science, the invention of new methods for the creation of carbon\u2013fluorine bonds is an important objective. Among the underdeveloped dimensions in this area are the fluorination of hindered alkyl halides (particularly chlorides) and the discovery of catalysts for such fluorination processes. Herein, we report a mild method for the fluorination of unactivated tertiary alkyl chlorides (and bromides), catalyzed by inexpensive PPh\u2083. This straightforward process is compatible with a range of hindered electrophiles and a variety of functional groups.
", "date": "2023-11-22", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "145", "number": "46", "publisher": "American Chemical Society", "pagerange": "25093-25097", "issn": "0002-7863", "official_url": "https://authors.library.caltech.edu/records/qkc4v-vzc32", "funders": { "items": [ { "grant_number": "R35-GM145315" }, { "agency": "Beckman Institute, California Institute of Technology" }, {}, { "agency": "Dow Next-Generation Educator Fund" } ] }, "doi": "10.1021/jacs.3c11042", "primary_object": { "basename": "ja3c11042_si_001.pdf", "url": "https://authors.library.caltech.edu/records/qkc4v-vzc32/files/ja3c11042_si_001.pdf" }, "resource_type": "article", "pub_year": "2023", "author_list": "Wang, Zhuo-Yan; Freas, Dylan J.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/g677n-tbn19", "eprint_id": 122407, "eprint_status": "archive", "datestamp": "2023-08-22 21:17:35", "lastmod": "2023-10-20 20:31:49", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Tong-Xiaoyu", "name": { "family": "Tong", "given": "Xiaoyu" }, "orcid": "0000-0002-1343-6335" }, { "id": "Yang-Ze\u2010Peng", "name": { "family": "Yang", "given": "Ze\u2010Peng" } }, { "id": "Del-Angel-Aguilar-Carlos-E", "name": { "family": "Del Angel Aguilar", "given": "Carlos E." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Iron\u2010Catalyzed Reductive Cross\u2010Coupling of Alkyl Electrophiles with Olefins", "ispublished": "pub", "full_text_status": "public", "keywords": "General Chemistry; Catalysis", "note": "\u00a9 2023 Wiley-VCH GmbH. \n\nWe thank Robert L. Anderson, Dr. Caiyou Chen, Hyungdo Cho, Dr. Dylan\u2005J. Freas, Dr. Asik Hossain, and Christian Johansen for assistance and helpful discussions. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences; grant R35-GM145315), the Resnick Sustainability Institute, the John Stauffer Fund (support for C.\u2005E.\u2005D.\u2005A.), the Beckman Institute (support of the EPR facility and the Center for Catalysis and Chemical Synthesis), the Gordon and Betty Moore Foundation (support of the Center for Catalysis and Chemical Synthesis), the Dow Next-Generation Educator Fund (grant to the California Institute of Technology), and the Peters laboratory (M\u00f6ssbauer spectrometer). \n\nData Availability Statement: The data that support the findings of this study are available in the Supporting Information of this article. \n\nThe authors declare no conflict of interest.\n\nSupplemental Material - anie202306663-sup-0001-misc_information.pdf
", "abstract": "In terms of its abundance and its minimal toxicity, iron has advantages relative to other transition metals. Although alkyl\u2013alkyl bond construction is central to organic synthesis, examples of iron-catalyzed alkyl\u2013alkyl couplings of alkyl electrophiles are relatively sparse. Herein we report an iron catalyst that achieves cross-coupling reactions of alkyl electrophiles wherein olefins, in the presence of a hydrosilane, are used in place of alkylmetal reagents. Carbon\u2013carbon bond formation proceeds at room temperature, and the method employs commercially available components (Fe(OAc)\u2082, Xantphos, and Mg(OEt)\u2082); interestingly, this set of reagents can be applied directly to a distinct hydrofunctionalization of olefins, hydroboration. Mechanistic studies are consistent with the generation of an alkyl radical from the alkyl electrophile, as well as with reversibility for elementary steps that precede carbon\u2013carbon bond formation (olefin binding to iron and \u03b2-migratory insertion).", "date": "2023-08-16", "date_type": "published", "publication": "Angewandte Chemie International Edition", "publisher": "Wiley", "pagerange": "Art. No. e202306663", "id_number": "CaltechAUTHORS:20230725-746869000.33", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20230725-746869000.33", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R35-GM145315" }, { "agency": "Resnick Sustainability Institute" }, { "agency": "John Stauffer Fund" }, { "agency": "Caltech Beckman Institute" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "Dow Next Generation Education Fund" } ] }, "local_group": { "items": [ { "id": "Resnick-Sustainability-Institute" } ] }, "doi": "10.1002/anie.202306663", "primary_object": { "basename": "anie202306663-sup-0001-misc_information.pdf", "url": "https://authors.library.caltech.edu/records/g677n-tbn19/files/anie202306663-sup-0001-misc_information.pdf" }, "resource_type": "article", "pub_year": "2023", "author_list": "Tong, Xiaoyu; Yang, Ze\u2010Peng; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/t9vkj-5gp94", "eprint_id": 121914, "eprint_status": "archive", "datestamp": "2023-08-22 21:07:23", "lastmod": "2023-10-20 16:47:48", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Chen-Caiyou", "name": { "family": "Chen", "given": "Caiyou" }, "orcid": "0000-0001-7536-7139" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Copper-catalysed enantioconvergent alkylation of oxygen nucleophiles", "ispublished": "pub", "full_text_status": "public", "keywords": "Multidisciplinary", "note": "\u00a9 The Author(s), under exclusive licence to Springer Nature Limited 2023. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, R01\u2013GM109194 and R35\u2013GM145315), the Beckman Institute (support for the Caltech Center for Catalysis and Chemical Synthesis, EPR Facility and X-ray Crystallography Facility), the Dow Next-Generation Educator Fund (grant to Caltech) and Boehringer\u2013Ingelheim Pharmaceuticals. We thank R. Anderson, H. Cho, S. Munoz, P. H. Oyala, F. Schneck, M. K. Takase and X. Tong for assistance and discussions. \n\nContributions. C.C. performed all experiments. C.C. and G.C.F. wrote the paper. Both authors contributed to the analysis and the interpretation of the results. \n\nData availability. The data that support the findings of this study are available within the paper, its Supplementary Information (experimental procedures and characterization data) and from the Cambridge Crystallographic Data Centre (https://www.ccdc.cam.ac.uk/structures; crystallographic data are available free of charge under CCDC reference numbers CCDC 2192280\u20132192286). \n\nThe authors declare no competing interests.", "abstract": "Carbon\u2013oxygen bonds are commonplace in organic molecules, including chiral bioactive compounds; therefore, the development of methods for their construction with simultaneous control of stereoselectivity is an important objective in synthesis. The Williamson ether synthesis, first reported in 1850, is the most widely used approach to the alkylation of an oxygen nucleophile, but it has significant limitations (scope and stereochemistry) owing to its reaction mechanism (SN2 pathway). Transition-metal catalysis of the coupling of an oxygen nucleophile with an alkyl electrophile has the potential to address these limitations, but progress so far has been limited, especially with regard to controlling enantioselectivity. Here we establish that a readily available copper catalyst can achieve an array of enantioconvergent substitution reactions of \u03b1-haloamides, a useful family of electrophiles, by oxygen nucleophiles; the reaction proceeds under mild conditions in the presence of a wide variety of functional groups. The catalyst is uniquely effective in being able to achieve enantioconvergent alkylations of not only oxygen nucleophiles but also nitrogen nucleophiles, giving support for the potential of transition-metal catalysts to provide a solution to the pivotal challenge of achieving enantioselective alkylations of heteroatom nucleophiles.", "date": "2023-06-08", "date_type": "published", "publication": "Nature", "volume": "618", "number": "7964", "publisher": "Nature Publishing Group", "pagerange": "301-307", "id_number": "CaltechAUTHORS:20230615-812791000.10", "issn": "0028-0836", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20230615-812791000.10", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM109194" }, { "agency": "NIH", "grant_number": "R35-GM145315" }, { "agency": "Caltech Beckman Institute" }, { "agency": "Dow Next Generation Educator Fund" }, { "agency": "Boehringer-Ingelheim" } ] }, "doi": "10.1038/s41586-023-06001-y", "resource_type": "article", "pub_year": "2023", "author_list": "Chen, Caiyou and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/a00b7-k6834", "eprint_id": 120005, "eprint_status": "archive", "datestamp": "2023-08-22 19:01:42", "lastmod": "2023-10-25 16:49:05", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Zuccarello-Giuseppe", "name": { "family": "Zuccarello", "given": "Giuseppe" }, "orcid": "0000-0001-6644-9300" }, { "id": "Batiste-Suzanne-M", "name": { "family": "Batiste", "given": "Suzanne M." }, "orcid": "0000-0003-2150-7516" }, { "id": "Cho-Hyungdo", "name": { "family": "Cho", "given": "Hyungdo" }, "orcid": "0000-0001-6109-5742" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Enantioselective Synthesis of \u03b1-Aminoboronic Acid Derivatives via Copper-Catalyzed N-Alkylation", "ispublished": "pub", "full_text_status": "public", "keywords": "Colloid and Surface Chemistry; Biochemistry; General Chemistry; Catalysis", "note": "\u00a9 2023 American Chemical Society. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences; grants R35-GM145315 to G.C.F. and F32-GM131595 to S.M.B.), the Swiss National Science Foundation (Grant P2SKP2_191321 to G.Z.), the Korea Foundation for Advanced Studies (graduate research fellowship to H.C.), and the Dow Next-Generation Educator Fund (grant to Caltech). We thank Dr. Caiyou Chen, Dr. Jaika D\u00f6rfler, Dr. Asik Hossain, Christian M. Johansen, Dr. Carson D. Matier, Dr. Paul H. Oyala, Dr. Felix Schneck, Dr. Mona Shahgholi, Dr. Hidehiro Suematsu, Dr. Michael K. Takase, Xiaoyu Tong, Dr. David G. VanderVelde, Dr. Scott C. Virgil, Zhuoyan Wang, and Dr. Feng Zhong for assistance and helpful discussions. \n\nThe authors declare no competing financial interest.", "abstract": "Due to burgeoning interest in the pharmaceutical industry in exploiting optically active \u03b1-aminoboronic derivatives as bioisosteres of \u03b1-amino acid derivatives, the discovery of methods for their catalytic asymmetric synthesis is an important challenge. Herein, we establish that a chiral copper catalyst (generated in situ from commercially available components) can achieve the enantioselective synthesis of \u03b1-aminoboronic derivatives via the coupling of two readily available partners, a carbamate and a racemic \u03b1-chloroboronate ester. Furthermore, we describe mechanistic studies that played a key role in the development of this new method and that provide insight into the optimized process.", "date": "2023-02-15", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "145", "number": "6", "publisher": "American Chemical Society", "pagerange": "3330-3334", "id_number": "CaltechAUTHORS:20230314-844891400.19", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20230314-844891400.19", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R35 GM145315" }, { "agency": "NIH Postdoctoral Fellowship", "grant_number": "F32 GM131595" }, { "agency": "Swiss National Science Foundation (SNSF)", "grant_number": "P2SKP2_191321" }, { "agency": "Korea Foundation for Advanced Studies" }, { "agency": "Dow Next Generation Educator Fund" } ] }, "doi": "10.1021/jacs.3c00038", "resource_type": "article", "pub_year": "2023", "author_list": "Zuccarello, Giuseppe; Batiste, Suzanne M.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/tz3m1-1c941", "eprint_id": 116148, "eprint_status": "archive", "datestamp": "2023-09-29 21:35:13", "lastmod": "2024-01-18 23:13:10", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Tong-Xiaoyu", "name": { "family": "Tong", "given": "Xiaoyu" } }, { "id": "Schneck-Felix", "name": { "family": "Schneck", "given": "Felix" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Catalytic Enantioselective \u03b1-Alkylation of Amides by Unactivated Alkyl Electrophiles", "ispublished": "pub", "full_text_status": "public", "keywords": "Alkyls, Carbonyls, Catalysts, Electrophiles, Reagents; Colloid and Surface Chemistry; Biochemistry; General Chemistry; Catalysis", "note": "\u00a9 2022 American Chemical Society. \n\nReceived 10 June 2022. Published online 4 August 2022. \n\nThis work is dedicated to the memory of Prof. David A. Evans. We thank Dr. Haohua Huo, Arianna Ayonon, and Dr. Zhaobin Wang for preliminary experiments, and we acknowledge Robert L. Anderson, Dr. Caiyou Chen, Hyungdo Cho, Dr. Dylan J. Freas, Dr. Lawrence M. Henling, Zachary P. Ifkovits, Dr. Mona Shahgholi, Dr. Michael K. Takase, Dr. David G. Vander Velde, Dr. Zepeng Yang, and Wendy Zhang for assistance and helpful discussions. Funding: Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grants R01-GM62871 and R35-GM145315), the Alexander von Humboldt Foundation (research fellowship for F.S.), the Beckman Institute (support of the Center for Catalysis and Chemical Synthesis, the EPR facility, the Molecular Materials Research Center, and the X-ray crystallography facility), the Gordon and Betty Moore Foundation (support of the Center for Catalysis and Chemical Synthesis), and the Dow Next-Generation Educator Fund (grant to the California Institute of Technology). \n\nAuthor Contributions. X.T. and F S. contributed equally. \n\nThe authors declare no competing financial interest.\n\nAccession Codes:\nCCDC 2150649\u22122150650 and 2150652\u22122150653 contain the\nsupplementary crystallographic data for this paper.\n\nSupplemental Material - ja2c06154_si_001.pdf
", "abstract": "Carbonyl groups that bear an \u03b1 stereocenter are commonly found in bioactive compounds, and intense effort has therefore been dedicated to the pursuit of stereoselective methods for constructing this motif. While the chiral auxiliary-enabled coupling of enolates with alkyl electrophiles represented groundbreaking progress in addressing this challenge, the next advance in the evolution of this enolate\u2013alkylation approach would be to use a chiral catalyst to control stereochemistry. Herein we describe the achievement of this objective, demonstrating that a nickel catalyst can accomplish enantioselective intermolecular alkylations of racemic Reformatsky reagents with unactivated electrophiles; the resulting \u03b1-alkylated carbonyl compounds can be converted in one additional step into a diverse array of ubiquitous families of chiral molecules. Applying a broad spectrum of mechanistic tools, we have gained insight into key intermediates (including the alkylnickel(II) resting state) and elementary steps of the catalytic cycle.", "date": "2022-08-17", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "144", "number": "32", "publisher": "American Chemical Society", "pagerange": "14856-14863", "id_number": "CaltechAUTHORS:20220805-758034000", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20220805-758034000", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01GM62871" }, { "agency": "NIH", "grant_number": "R35GM145315" }, { "agency": "Alexander von Humboldt Foundation" }, { "agency": "Caltech Beckman Institute" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "Dow Next Generation Educator Fund" } ] }, "doi": "10.1021/jacs.2c06154", "pmcid": "PMC10079215", "primary_object": { "basename": "nihms-1887223.pdf", "url": "https://authors.library.caltech.edu/records/tz3m1-1c941/files/nihms-1887223.pdf" }, "related_objects": [ { "basename": "ja2c06154_si_001.pdf", "url": "https://authors.library.caltech.edu/records/tz3m1-1c941/files/ja2c06154_si_001.pdf" } ], "resource_type": "article", "pub_year": "2022", "author_list": "Tong, Xiaoyu; Schneck, Felix; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/6570f-zs409", "eprint_id": 113767, "eprint_status": "archive", "datestamp": "2023-08-22 14:36:40", "lastmod": "2023-12-22 21:44:18", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Cho-Hyungdo", "name": { "family": "Cho", "given": "Hyungdo" }, "orcid": "0000-0001-6109-5742" }, { "id": "Suematsu-Hidehiro", "name": { "family": "Suematsu", "given": "Hidehiro" }, "orcid": "0000-0002-9444-7254" }, { "id": "Oyala-Paul-H", "name": { "family": "Oyala", "given": "Paul H." }, "orcid": "0000-0002-8761-4667" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Photoinduced, Copper-Catalyzed Enantioconvergent Alkylations of Anilines by Racemic Tertiary Electrophiles: Synthesis and Mechanism", "ispublished": "pub", "full_text_status": "public", "keywords": "Anions, Substitution reactions, Catalysts, Electrophiles, Alkyls; Colloid and Surface Chemistry; Biochemistry; General Chemistry; Catalysis", "note": "\u00a9 2022 American Chemical Society. \n\nReceived 3 December 2021. Published online 7 March 2022. \n\nThis study is dedicated to Prof. K. Barry Sharpless on the occasion of his 80th birthday. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM109194), the Korea Foundation for Advanced Studies (graduate research fellowship to H.C.), the National Science Foundation (support of the Caltech EPR Facility; NSF-1531940), the Arnold and Mabel Beckman Foundation (support of the Beckman Institute Laser Resource Center and the Molecular Materials Resource Center), and the Dow Next-Generation Educator Fund (grant to Caltech). We thank Dr. Bruce S. Brunschwig (Molecular Materials Resource Center), Dr. Mona Shahgoli (Mass Spectroscopy Facility), Dr. Michael K. Takase (X-ray Crystallography Facility), Dr. David Vander Velde (NMR Facility), Dr. Scott C. Virgil (Center for Catalysis and Chemical Synthesis), Dr. Jay R. Winkler (Beckman Institute Laser Resource Center), Dr. Caiyou Chen, Dr. Heejun Lee, Dr. Felix Schneck, Dr. Cooper Citek, Dr. Jaika D\u00f6rfler, Dr. Dylan J. Freas, Dr. Pablo Garrido Barros, Dr. Giuseppe Zuccarello, Dr. Suzanne M. Batiste, Christian M. Johansen, and Ammar Ibrahim for technical assistance and/or helpful discussions. \n\nThe authors declare no competing financial interest. \n\nAccession Codes: CCDC 2098015\u20132098016, 2098018\u20132098019, 2098022, and 2125108 contain the supplementary crystallographic data for this paper.\n\nAccepted Version - nihms-1812912.pdf
Supplemental Material - ja1c12749_si_001.pdf
", "abstract": "Transition-metal catalysis of substitution reactions of alkyl electrophiles by nitrogen nucleophiles is beginning to emerge as a powerful strategy for synthesizing higher-order amines, as well as controlling their stereochemistry. Herein, we report that a readily accessible chiral copper catalyst (commercially available components) can achieve the photoinduced, enantioconvergent coupling of a variety of racemic tertiary alkyl electrophiles with aniline nucleophiles to generate a new C\u2013N bond with good ee at the fully substituted stereocenter of the product; whereas this photoinduced, copper-catalyzed coupling proceeds at \u221278 \u00b0C, in the absence of light and catalyst, virtually no C\u2013N bond formation is observed even upon heating to 80 \u00b0C. The mechanism of this new catalytic enantioconvergent substitution process has been interrogated with the aid of a wide array of tools, including the independent synthesis of proposed intermediates and reactivity studies, spectroscopic investigations featuring photophysical and EPR data, and DFT calculations. These studies led to the identification of three copper-based intermediates in the proposed catalytic cycle, including a chiral three-coordinate formally copper(II)\u2013anilido (DFT analysis points to its formulation as a copper(I)\u2013anilidyl radical) complex that serves as a persistent radical that couples with a tertiary organic radical to generate the desired C\u2013N bond with good enantioselectivity.", "date": "2022-03-16", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "144", "number": "10", "publisher": "American Chemical Society", "pagerange": "4550-4558", "id_number": "CaltechAUTHORS:20220307-188438000", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20220307-188438000", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01 GM109194" }, { "agency": "Korea Foundation for Advanced Studies" }, { "agency": "NSF", "grant_number": "CHE-1531940" }, { "agency": "Arnold and Mabel Beckman Foundation" }, { "agency": "Dow Next Generation Educator Fund" } ] }, "doi": "10.1021/jacs.1c12749", "pmcid": "PMC9239302", "primary_object": { "basename": "nihms-1812912.pdf", "url": "https://authors.library.caltech.edu/records/6570f-zs409/files/nihms-1812912.pdf" }, "related_objects": [ { "basename": "ja1c12749_si_001.pdf", "url": "https://authors.library.caltech.edu/records/6570f-zs409/files/ja1c12749_si_001.pdf" } ], "resource_type": "article", "pub_year": "2022", "author_list": "Cho, Hyungdo; Suematsu, Hidehiro; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/pdg32-gfd78", "eprint_id": 113477, "eprint_status": "archive", "datestamp": "2023-08-22 14:31:31", "lastmod": "2023-12-22 21:49:41", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lee-Heejun", "name": { "family": "Lee", "given": "Heejun" }, "orcid": "0000-0002-0439-3863" }, { "id": "Ahn-Jun-Myun", "name": { "family": "Ahn", "given": "Jun Myun" } }, { "id": "Oyala-Paul-H", "name": { "family": "Oyala", "given": "Paul H." }, "orcid": "0000-0002-8761-4667" }, { "id": "Citek-Cooper", "name": { "family": "Citek", "given": "Cooper" }, "orcid": "0000-0001-9376-8200" }, { "id": "Yin-Haolin", "name": { "family": "Yin", "given": "Haolin" }, "orcid": "0000-0002-2063-8605" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Investigation of the C\u2013N Bond-Forming Step in a Photoinduced, Copper-Catalyzed Enantioconvergent N\u2013Alkylation: Characterization and Application of a Stabilized Organic Radical as a Mechanistic Probe", "ispublished": "pub", "full_text_status": "public", "keywords": "Colloid and Surface Chemistry; Biochemistry; General Chemistry; Catalysis", "note": "\u00a9 2022 American Chemical Society. \n\nReceived 14 December 2021. Published online 15 February 2022. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-109194). We are grateful to the Dow Innovation Fund for support of our EPR facility and to the Beckman Institute X-ray Crystallography Facility. The Resnick Sustainability Institute at Caltech is acknowledged for its support of enabling facilities. J.M.A. acknowledges the National Sciences and Engineering Research Council (NSERC) of Canada for a graduate research fellowship. J.C.P. and G.C.F. dedicate this contribution to the memory of our colleague, mentor, and friend Robert H. Grubbs. \n\nThe authors declare no competing financial interest. \n\nCCDC 2128476\u20132128480 contain the supplementary crystallographic data for this paper.\n\nAccepted Version - nihms-1820516.pdf
Supplemental Material - ja1c13151_si_001.pdf
Supplemental Material - ja1c13151_si_002.txt
", "abstract": "Whereas photoinduced, copper-catalyzed couplings of nitrogen nucleophiles with alkyl electrophiles have recently been shown to provide an attractive approach to achieving a variety of enantioselective C\u2013N bond constructions, mechanistic studies of these transformations have lagged the advances in reaction development. Herein we provide mechanistic insight into a previously reported photoinduced, copper-catalyzed enantioconvergent C\u2013N coupling of a carbazole nucleophile with a racemic tertiary \u03b1-haloamide electrophile. Building on the isolation of a copper(II) model complex whose EPR parameters serve as a guide, we independently synthesize two key intermediates in the proposed catalytic cycle, a copper(II) metalloradical (L*Cu^(II)(carb\u2032)\u2082) (L* = a monodentate chiral phosphine ligand; carb\u2032 = a carbazolide ligand), as well as a tertiary \u03b1-amide organic radical (R\u00b7); the generation and characterization of R\u00b7 was guided by DFT calculations, which suggested that it would be stable to homocoupling. Continuous-wave (CW) and pulse EPR studies, along with corresponding DFT calculations, are among the techniques used to characterize these reactive radicals. We establish that these two radicals do indeed combine to furnish the C\u2013N coupling product in good yield and with significant enantiomeric excess (77% yield, 55% ee), thereby supporting the chemical competence of these proposed intermediates. DFT calculations are consistent with R\u00b7 initially binding to copper(II) via a dative interaction from the closed-shell carbonyl oxygen atom of the radical, which positions the \u03b1-carbon for direct reaction with the copper(II)-bound carbazole N atom, to generate the C\u2013N bond with enantioselectivity, without the formation of an alkylcopper(III) intermediate.", "date": "2022-03-09", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "144", "number": "9", "publisher": "American Chemical Society", "pagerange": "4114-4123", "id_number": "CaltechAUTHORS:20220216-527740512", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20220216-527740512", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01109194" }, { "agency": "Dow Innovation Fund" }, { "agency": "Resnick Sustainability Institute" }, { "agency": "Natural Sciences and Engineering Research Council of Canada (NSERC)" } ] }, "local_group": { "items": [ { "id": "Resnick-Sustainability-Institute" } ] }, "doi": "10.1021/jacs.1c13151", "pmcid": "PMC9269863", "primary_object": { "basename": "nihms-1820516.pdf", "url": "https://authors.library.caltech.edu/records/pdg32-gfd78/files/nihms-1820516.pdf" }, "related_objects": [ { "basename": "ja1c13151_si_001.pdf", "url": "https://authors.library.caltech.edu/records/pdg32-gfd78/files/ja1c13151_si_001.pdf" }, { "basename": "ja1c13151_si_002.txt", "url": "https://authors.library.caltech.edu/records/pdg32-gfd78/files/ja1c13151_si_002.txt" } ], "resource_type": "article", "pub_year": "2022", "author_list": "Lee, Heejun; Ahn, Jun Myun; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/fb7fd-s7v25", "eprint_id": 109283, "eprint_status": "archive", "datestamp": "2023-08-22 10:51:16", "lastmod": "2023-10-23 17:48:05", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Chen-Caiyou", "name": { "family": "Chen", "given": "Caiyou" }, "orcid": "0000-0001-7536-7139" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Photoinduced copper-catalysed asymmetric amidation via ligand cooperativity", "ispublished": "pub", "full_text_status": "public", "keywords": "Asymmetric catalysis; Asymmetric synthesis; Catalytic mechanisms; Synthetic chemistry methodology; Photocatalysis", "note": "\u00a9 The Author(s), under exclusive licence to Springer Nature Limited 2021. \n\nReceived 21 February 2021; Accepted 16 June 2021; Published 28 June 2021. \n\nThis manuscript is dedicated to the memory of Gregory P. Harlow. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, R01-GM109194), the Beckman Institute (support of the Laser Resource Center, as well as the Center for Catalysis and Chemical Synthesis, the EPR facility, and the X-ray crystallography facility), the Gordon and Betty Moore Foundation (support for the Center for Catalysis and Chemical Synthesis), the Dow Next-Generation Educator Fund (grant to Caltech) and Boehringer\u2013Ingelheim Pharmaceuticals. We thank C. Citek, T. M. Donnell, J. D\u00f8rfler, P. Garrido Barros, L. M. Henling, P. H. Oyala, F. Schneck, M. Shahgoli, D. VanderVelde and J. R. Winkler for assistance and discussions. \n\nData availability: The data that support the findings of this study are available within the paper, its Supplementary Information (experimental procedures and characterization data) and from the Cambridge Crystallographic Data Centre (https://www.ccdc.cam.ac.uk/structures; crystallographic data are available free of charge under CCDC reference numbers CCDC 2055329\u20132055338). \n\nAuthor Contributions: C.C. performed all experiments. C.C., J.C.P. and G.C.F. wrote the manuscript. All authors contributed to the analysis and the interpretation of the results. \n\nThe authors declare no competing interests.\n \nPeer review information: Nature thanks the anonymous reviewers for their contribution to the peer review of this work.\n\nSupplemental Material - 41586_2021_3730_MOESM1_ESM.pdf
", "abstract": "The substitution of an alkyl electrophile by a nucleophile is a foundational reaction in organic chemistry that enables the efficient and convergent synthesis of organic molecules. Whereas substantial progress has been reported in recent years in exploiting transition-metal catalysis to dramatically expand the scope of nucleophilic substitution reactions using carbon nucleophiles, there has been limited progress in corresponding reactions with nitrogen nucleophiles. Furthermore, for many substitution reactions, the bond construction itself is not the only challenge, as there is a need to control stereochemistry at the same time. Here we describe a method for the enantioconvergent substitution of unactivated racemic alkyl electrophiles by a ubiquitous nitrogen-containing functional group, an amide, through the use of a photoinduced catalyst system based on copper, an earth-abundant metal. This process for asymmetric N-alkylation relies upon three distinct ligands: a bisphosphine, a phenoxide and a chiral diamine, that assemble, in situ, a copper/bisphosphine/phenoxide complex that serves as a photocatalyst and a chiral copper/diamine complex that catalyzes enantioselective C\u2013N bond formation. This study thus expands enantioselective N-substitution by alkyl electrophiles beyond activated electrophiles (those bearing at least one sp- or sp\u00b2-hybridized substituent on the carbon undergoing substitution) to include unactivated electrophiles.", "date": "2021-08-12", "date_type": "published", "publication": "Nature", "volume": "596", "number": "7871", "publisher": "Nature Publishing Group", "pagerange": "250-256", "id_number": "CaltechAUTHORS:20210527-133944938", "issn": "0028-0836", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20210527-133944938", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM109194" }, { "agency": "Caltech Beckman Institute" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "Dow Next Generation Educator Fund" }, { "agency": "Boehringer-Ingelheim Pharmaceuticals" } ] }, "doi": "10.1038/s41586-021-03730-w", "pmcid": "PMC8363576", "primary_object": { "basename": "41586_2021_3730_MOESM1_ESM.pdf", "url": "https://authors.library.caltech.edu/records/fb7fd-s7v25/files/41586_2021_3730_MOESM1_ESM.pdf" }, "resource_type": "article", "pub_year": "2021", "author_list": "Chen, Caiyou; Peters, Jonas C.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/nstpb-32029", "eprint_id": 109385, "eprint_status": "archive", "datestamp": "2023-08-20 03:43:04", "lastmod": "2023-10-23 17:54:13", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Yang-Ze-Peng", "name": { "family": "Yang", "given": "Ze-Peng" }, "orcid": "0000-0003-0248-1963" }, { "id": "Freas-Dylan-J", "name": { "family": "Freas", "given": "Dylan J." }, "orcid": "0000-0003-0611-7907" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Asymmetric Synthesis of Protected Unnatural \u03b1-Amino Acids via Enantioconvergent Nickel-Catalyzed Cross-Coupling", "ispublished": "pub", "full_text_status": "public", "keywords": "Reagents, Enantioselective synthesis, Electrophiles, Alkyls, Cross coupling reaction", "note": "\u00a9 2021 American Chemical Society. \n\nReceived: April 14, 2021; Published: June 3, 2021. \n\nThis paper is dedicated to Professor David A. Evans on the occasion of his 80th birthday. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences; grant R01-GM062871), the National Science Foundation Graduate Research Fellowship Program (grant DGE-1745301), and the Dow Next-Generation Educator Fund (grant to Caltech). We thank Lawrence M. Henling and Dr. Michael K. Takase (Caltech X-Ray Crystallography Facility), Dr. Asik Hossain, Dr. Paul H. Oyala (Caltech EPR Facility), Dr. Felix Schneck, Dr. David G. VanderVelde (Caltech NMR Facility), and Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis) for assistance and helpful discussions. \n\nAuthor Contributions. Z.-P.Y. and D.J.F. contributed equally. \n\nThe authors declare no competing financial interest. \n\nAccession Codes. CCDC 2072620 contains the supplementary crystallographic data for this paper.\n\nAccepted Version - nihms-1729859.pdf
Supplemental Material - ja1c03903_si_001.pdf
", "abstract": "Interest in unnatural \u03b1-amino acids has increased rapidly in recent years in areas ranging from protein design to medicinal chemistry to materials science. Consequently, the development of efficient, versatile, and straightforward methods for their enantioselective synthesis is an important objective in reaction development. In this report, we establish that a chiral catalyst based on nickel, an earth-abundant metal, can achieve the enantioconvergent coupling of readily available racemic alkyl electrophiles with a wide variety of alkylzinc reagents (1:1.1 ratio) to afford protected unnatural \u03b1-amino acids in good yield and ee. This cross-coupling, which proceeds under mild conditions and is tolerant of air, moisture, and a broad array of functional groups, complements earlier approaches to the catalytic asymmetric synthesis of this valuable family of molecules. We have applied our new method to the generation of several enantioenriched unnatural \u03b1-amino acids that have previously been shown to serve as useful intermediates in the synthesis of bioactive compounds.", "date": "2021-06-16", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "143", "number": "23", "publisher": "American Chemical Society", "pagerange": "8614-8618", "id_number": "CaltechAUTHORS:20210604-111535270", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20210604-111535270", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM062871" }, { "agency": "NSF Graduate Research Fellowship", "grant_number": "DGE-1745301" }, { "agency": "Dow Next Generation Educator Fund" } ] }, "doi": "10.1021/jacs.1c03903", "pmcid": "PMC8351905", "primary_object": { "basename": "ja1c03903_si_001.pdf", "url": "https://authors.library.caltech.edu/records/nstpb-32029/files/ja1c03903_si_001.pdf" }, "related_objects": [ { "basename": "nihms-1729859.pdf", "url": "https://authors.library.caltech.edu/records/nstpb-32029/files/nihms-1729859.pdf" } ], "resource_type": "article", "pub_year": "2021", "author_list": "Yang, Ze-Peng; Freas, Dylan J.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/vkjyy-vay13", "eprint_id": 107393, "eprint_status": "archive", "datestamp": "2023-08-20 02:02:26", "lastmod": "2023-10-23 15:50:55", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Wang-Zhaobin", "name": { "family": "Wang", "given": "Zhaobin" }, "orcid": "0000-0001-7934-2879" }, { "id": "Yang-Ze-Peng", "name": { "family": "Yang", "given": "Ze-Peng" }, "orcid": "0000-0003-0248-1963" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Quaternary stereocentres via catalytic enantioconvergent nucleophilic substitution reactions of tertiary alkyl halides", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2020 Nature Publishing Group. \n\nReceived 12 January 2020; Accepted 18 November 2020; Published 11 January 2021. \n\nThis paper is dedicated to the memory of Professor Jonathan Williams (University of Bath). Support has been provided by the NIGMS (R37-GM62871) and the Dow Next Generation Educator Fund (grant to Caltech). We thank S.M. Batiste, L.M. Henling, H. Huo, F. Schneck, M.K. Takase, S.C. Virgil and W. Zhang for assistance and helpful discussions. \n\nData availability: The data that support the findings of this study are available in the Supplementary Information (experimental procedures and characterization data). Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 1958912 (13), 1958913 (81), and 1965146 (80). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. \n\nAuthor Contributions: Z.W. and Z.-P.Y. performed all experiments. Z.W. and G.C.F. wrote the manuscript. All authors contributed to the analysis and the interpretation of the results. \n\nThe authors declare no competing interests.\n\nSupplemental Material - 41557_2020_609_MOESM172_ESM.pdf
Supplemental Material - 41557_2020_609_MOESM173_ESM.cif
Supplemental Material - 41557_2020_609_MOESM174_ESM.cif
Supplemental Material - 41557_2020_609_MOESM175_ESM.cif
", "abstract": "The development of efficient methods, particularly catalytic and enantioselective processes, for the construction of all-carbon quaternary stereocentres is an important (and difficult) challenge in organic synthesis due to the occurrence of this motif in a range of bioactive molecules. One conceptually straightforward and potentially versatile approach is the catalytic enantioconvergent substitution reaction of a readily available racemic tertiary alkyl electrophile by an organometallic nucleophile; however, examples of such processes are rare. Here we demonstrate that a nickel-based chiral catalyst achieves enantioconvergent couplings of a variety of tertiary electrophiles (cyclic and acyclic \u03b1-halocarbonyl compounds) with alkenylmetal nucleophiles to form quaternary stereocentres with good yield and enantioselectivity under mild conditions in the presence of a range of functional groups. These couplings, which probably proceed via a radical pathway, provide access to an array of useful families of organic compounds, including intermediates in the total synthesis of two natural products, (\u2013)-eburnamonine and madindoline A.", "date": "2021-03", "date_type": "published", "publication": "Nature Chemistry", "volume": "13", "number": "3", "publisher": "Nature Publishing Group", "pagerange": "236-242", "id_number": "CaltechAUTHORS:20210111-120204779", "issn": "1755-4330", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20210111-120204779", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R37-GM62871" }, { "agency": "Dow Next Generation Educator Fund" } ] }, "doi": "10.1038/s41557-020-00609-7", "primary_object": { "basename": "41557_2020_609_MOESM173_ESM.cif", "url": "https://authors.library.caltech.edu/records/vkjyy-vay13/files/41557_2020_609_MOESM173_ESM.cif" }, "related_objects": [ { "basename": "41557_2020_609_MOESM174_ESM.cif", "url": "https://authors.library.caltech.edu/records/vkjyy-vay13/files/41557_2020_609_MOESM174_ESM.cif" }, { "basename": "41557_2020_609_MOESM175_ESM.cif", "url": "https://authors.library.caltech.edu/records/vkjyy-vay13/files/41557_2020_609_MOESM175_ESM.cif" }, { "basename": "41557_2020_609_MOESM172_ESM.pdf", "url": "https://authors.library.caltech.edu/records/vkjyy-vay13/files/41557_2020_609_MOESM172_ESM.pdf" } ], "resource_type": "article", "pub_year": "2021", "author_list": "Wang, Zhaobin; Yang, Ze-Peng; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/15caw-y2838", "eprint_id": 108014, "eprint_status": "archive", "datestamp": "2023-08-20 01:57:16", "lastmod": "2023-10-23 16:24:26", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Yang-Ze-Peng", "name": { "family": "Yang", "given": "Ze-Peng" }, "orcid": "0000-0003-0248-1963" }, { "id": "Freas-Dylan-J", "name": { "family": "Freas", "given": "Dylan J." }, "orcid": "0000-0003-0611-7907" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "The Asymmetric Synthesis of Amines via Nickel-Catalyzed Enantioconvergent Substitution Reactions", "ispublished": "pub", "full_text_status": "public", "keywords": "Coupling reactions, Organic compounds, Alkyls, Substitution reactions, Enantioselective synthesis", "note": "\u00a9 2021 American Chemical Society. \n\nReceived: December 16, 2020; Published: February 10, 2021. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences; grant R01-GM062871), the National Science Foundation Graduate Research Fellowship Program (grant DGE-1745301 to D. J. F.), and the Dow Next-Generation Educator Fund (grant to Caltech). We thank Dr. Haohua Huo for important early contributions to this project, and we thank Nicholas J. Fastuca, Lawrence M. Henling and Dr. Michael K. Takase (Caltech X-Ray Crystallography Facility), Dr. Paul H. Oyala (Caltech EPR Facility), Dr. Felix Schneck, Xiaoyu Tong, Dr. David G. VanderVelde (Caltech NMR Facility), Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis), and Wanji Zhang for assistance and helpful discussions. \n\nAuthor Contributions. Z.-P.Y. and D.J.F. contributed equally. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms-1727151.pdf
Supplemental Material - ja0c13034_si_001.pdf
", "abstract": "Chiral dialkyl carbinamines are important in fields such as organic chemistry, pharmaceutical chemistry, and biochemistry, serving for example as bioactive molecules, chiral ligands, and chiral catalysts. Unfortunately, most catalytic asymmetric methods for synthesizing dialkyl carbinamines do not provide general access to amines wherein the two alkyl groups are of similar size (e.g., CH\u2082R versus CH\u2082R\u00b9). Herein, we report two mild methods for the catalytic enantioconvergent synthesis of protected dialkyl carbinamines, both of which use a chiral nickel catalyst to couple an alkylzinc reagent (1.1\u20131.2 equiv) with a racemic partner, specifically, an \u03b1-phthalimido alkyl chloride or an N-hydroxyphthalimide (NHP) ester of a protected \u03b1-amino acid. The methods are versatile, providing dialkyl carbinamine derivatives that bear an array of functional groups. For couplings of NHP esters, we further describe a one-pot variant wherein the NHP ester is generated in situ, allowing the generation of enantioenriched protected dialkyl carbinamines in one step from commercially available amino acid derivatives; we demonstrate the utility of this method by applying it to the efficient catalytic enantioselective synthesis of a range of interesting target molecules.", "date": "2021-02-24", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "143", "number": "7", "publisher": "American Chemical Society", "pagerange": "2930-2937", "id_number": "CaltechAUTHORS:20210211-151616006", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20210211-151616006", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM062871" }, { "agency": "NSF Graduate Research Fellowship", "grant_number": "DGE-1745301" }, { "agency": "Dow Next Generation Educator Fund" } ] }, "doi": "10.1021/jacs.0c13034", "pmcid": "PMC8336453", "primary_object": { "basename": "ja0c13034_si_001.pdf", "url": "https://authors.library.caltech.edu/records/15caw-y2838/files/ja0c13034_si_001.pdf" }, "related_objects": [ { "basename": "nihms-1727151.pdf", "url": "https://authors.library.caltech.edu/records/15caw-y2838/files/nihms-1727151.pdf" } ], "resource_type": "article", "pub_year": "2021", "author_list": "Yang, Ze-Peng; Freas, Dylan J.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/m192p-sav72", "eprint_id": 101936, "eprint_status": "archive", "datestamp": "2023-08-19 20:38:01", "lastmod": "2023-10-19 23:40:02", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Yang-Ze-Peng", "name": { "family": "Yang", "given": "Ze-Peng" }, "orcid": "0000-0003-0248-1963" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Convergent Catalytic Asymmetric Synthesis of Esters of Chiral Dialkyl Carbinols", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2020 American Chemical Society. \n\nReceived: February 3, 2020; Published: March 16, 2020. \n\nSupport was provided by the National Institutes of Health (National Institute of General Medical Sciences; grant R01-GM062871), the Shanghai Institute of Organic Chemistry (fellowship to Z.-P.Y.), and the Dow Next-Generation Educator Fund (grant to Caltech). We thank Dr. Caiyou Chen, Dr. Haohua Huo, Dr. Paul H. Oyala, Dr. David G. VanderVelde, Dr. Scott C. Virgil, and Dr. Zhaobin Wang for assistance and for helpful discussions. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms-1638615.pdf
Supplemental Material - ja0c01324_si_001.pdf
", "abstract": "Because chiral dialkyl carbinols, as well as their derived esters, are significant as intermediates and end points in fields such as organic, pharmaceutical, and biological chemistry, the development of efficient approaches to their asymmetric synthesis is an important endeavor. In this report, we describe a method for the direct catalytic enantioselective synthesis of such esters, beginning with an alkyl halide (derived from an aldehyde and an acyl bromide), an olefin, and a hydrosilane, catalyzed by nickel, an earth-abundant metal. The method is versatile, tolerating substituents that vary in size and that bear a range of functional groups. We further describe a four-component variant of this process, wherein the alkyl halide is generated in situ, thus obviating the need to isolate either an alkyl electrophile or an alkylmetal, while still effecting an alkyl\u2013alkyl coupling. Finally, we apply our convergent method to the efficient catalytic enantioselective synthesis of three esters that are bioactive themselves or that have been utilized in the synthesis of bioactive compounds.", "date": "2020-03-25", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "142", "number": "12", "publisher": "American Chemical Society", "pagerange": "5870-5875", "id_number": "CaltechAUTHORS:20200316-151135011", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200316-151135011", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM062871" }, { "agency": "Shanghai Institute of Organic Chemistry (SIOC)" }, { "agency": "Dow Next-Generation Education Fund" } ] }, "doi": "10.1021/jacs.0c01324", "pmcid": "PMC7580270", "primary_object": { "basename": "ja0c01324_si_001.pdf", "url": "https://authors.library.caltech.edu/records/m192p-sav72/files/ja0c01324_si_001.pdf" }, "related_objects": [ { "basename": "nihms-1638615.pdf", "url": "https://authors.library.caltech.edu/records/m192p-sav72/files/nihms-1638615.pdf" } ], "resource_type": "article", "pub_year": "2020", "author_list": "Yang, Ze-Peng and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/92n3d-9tc85", "eprint_id": 101007, "eprint_status": "archive", "datestamp": "2023-08-19 19:41:55", "lastmod": "2023-10-20 22:16:24", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Huo-Haohua", "name": { "family": "Huo", "given": "Haohua" } }, { "id": "Gorsline-Bradley-J", "name": { "family": "Gorsline", "given": "Bradley J." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Catalyst-controlled doubly enantioconvergent coupling of racemic alkyl nucleophiles and electrophiles", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2020 American Association for the Advancement of Science.\nThis is an article distributed under the terms of the Science Journals Default License. \n\nReceived 4 September 2019; accepted 26 November 2019. \n\nWe thank S. H. Jungbauer, S. C. Virgil, L. M. Henling, D. G. Vander Velde, H. Yin, D. J. Freas, W. Zhang, and Z. Yang for assistance and discussions. \n\nFunding: Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, R37-GM62871). H.H. thanks the Resnick Sustainability Institute at Caltech for fellowship support. \n \nAuthor contributions: H.H. and B.J.G. performed all experiments. H.H. and G.C.F. wrote the manuscript. All authors contributed to the analysis and the interpretation of the results. \n\nThe authors declare no competing interests. \n\nData and materials availability: The data that support the findings of this study are available in the paper, in its supplementary materials (experimental procedures and characterization data), and from the Cambridge Crystallographic Data Centre (CCDC) (www.ccdc.cam.ac.uk/structures; crystallographic data are available free of charge under CCDC reference numbers 1935944 and 1935945).\n\nAccepted Version - nihms-1566755.pdf
Supplemental Material - aaz3855_Huo_SM.pdf
", "abstract": "Stereochemical control in the construction of carbon-carbon bonds between an alkyl electrophile and an alkyl nucleophile is a persistent challenge in organic synthesis. Classical substitution reactions via S_N1 and S_N2 pathways are limited in their ability to generate carbon-carbon bonds (inadequate scope, due to side reactions such as rearrangements and eliminations) and to control stereochemistry when beginning with readily available racemic starting materials (racemic products). Here, we report a chiral nickel catalyst that couples racemic electrophiles (propargylic halides) with racemic nucleophiles (\u03b2-zincated amides) to form carbon-carbon bonds in doubly stereoconvergent processes, affording a single stereoisomer of the product from two stereochemical mixtures of reactants.", "date": "2020-01-31", "date_type": "published", "publication": "Science", "volume": "367", "number": "6477", "publisher": "American Association for the Advancement of Science", "pagerange": "559-564", "id_number": "CaltechAUTHORS:20200130-135407173", "issn": "0036-8075", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200130-135407173", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R37-GM62871" }, { "agency": "Resnick Sustainability Institute" } ] }, "local_group": { "items": [ { "id": "Resnick-Sustainability-Institute" } ] }, "doi": "10.1126/science.aaz3855", "pmcid": "PMC7566878", "primary_object": { "basename": "aaz3855_Huo_SM.pdf", "url": "https://authors.library.caltech.edu/records/92n3d-9tc85/files/aaz3855_Huo_SM.pdf" }, "related_objects": [ { "basename": "nihms-1566755.pdf", "url": "https://authors.library.caltech.edu/records/92n3d-9tc85/files/nihms-1566755.pdf" } ], "resource_type": "article", "pub_year": "2020", "author_list": "Huo, Haohua; Gorsline, Bradley J.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/09gnn-bwy58", "eprint_id": 98544, "eprint_status": "archive", "datestamp": "2023-08-19 17:58:46", "lastmod": "2023-10-18 17:27:10", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Yin-Haolin", "name": { "family": "Yin", "given": "Haolin" }, "orcid": "0000-0002-2063-8605" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Mechanistic Investigation of Enantioconvergent Kumada Reactions of Racemic \u03b1-Bromoketones Catalyzed by a Nickel/Bis(oxazoline) Complex", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2019 American Chemical Society. \n\nReceived: July 30, 2019; Published: September 10, 2019. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences; grant R01-GM062871). We thank Lawrence M. Henling, Dr. Paul H. Oyala, Dr. Michael K. Takase, Dr. Scott C. Virgil, Dr. Zhaobin Wang, and the laboratories of Prof. Jonas C. Peters and Prof. Theodor Agapie for assistance and for helpful discussions, and we acknowledge the Dow Next Generation Educator Fund for support of instrumentation at Caltech. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms-1557310.pdf
Supplemental Material - ja9b08185_si_002.cif
Supplemental Material - ja9b08185_si_003.pdf
", "abstract": "In recent years, a wide array of methods for achieving nickel-catalyzed substitution reactions of alkyl electrophiles by organometallic nucleophiles, including enantioconvergent processes, have been described; however, experiment-focused mechanistic studies of such couplings have been comparatively scarce. The most detailed mechanistic investigations to date have examined catalysts that bear tridentate ligands and, with one exception, processes that are not enantioselective; studies of catalysts based on bidentate ligands could be anticipated to be more challenging, due to difficulty in isolating proposed intermediates as a result of instability arising from coordinative unsaturation. In this investigation, we explore the mechanism of enantioconvergent Kumada reactions of racemic \u03b1-bromoketones catalyzed by a nickel complex that bears a bidentate chiral bis(oxazoline) ligand. Utilizing an array of mechanistic tools (including isolation and reactivity studies of three of the four proposed nickel-containing intermediates, as well as interrogation via EPR spectroscopy, UV\u2013vis spectroscopy, radical probes, and DFT calculations), we provide support for a pathway in which carbon\u2013carbon bond formation proceeds via a radical-chain process wherein a nickel(I) complex serves as the chain-carrying radical and an organonickel(II) complex is the predominant resting state of the catalyst. Computations indicate that the coupling of this organonickel(II) complex with an organic radical is the stereochemistry-determining step of the reaction.", "date": "2019-09-25", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "141", "number": "38", "publisher": "American Chemical Society", "pagerange": "15433-15440", "id_number": "CaltechAUTHORS:20190910-110659740", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20190910-110659740", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM062871" }, { "agency": "Dow Next Generation Educator Fund" } ] }, "doi": "10.1021/jacs.9b08185", "pmcid": "PMC7075318", "primary_object": { "basename": "ja9b08185_si_002.cif", "url": "https://authors.library.caltech.edu/records/09gnn-bwy58/files/ja9b08185_si_002.cif" }, "related_objects": [ { "basename": "ja9b08185_si_003.pdf", "url": "https://authors.library.caltech.edu/records/09gnn-bwy58/files/ja9b08185_si_003.pdf" }, { "basename": "nihms-1557310.pdf", "url": "https://authors.library.caltech.edu/records/09gnn-bwy58/files/nihms-1557310.pdf" } ], "resource_type": "article", "pub_year": "2019", "author_list": "Yin, Haolin and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/s7gby-4k828", "eprint_id": 98510, "eprint_status": "archive", "datestamp": "2023-08-19 17:54:30", "lastmod": "2023-10-20 22:14:23", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Bartoszewicz-Agnieszka", "name": { "family": "Bartoszewicz", "given": "Agnieszka" }, "orcid": "0000-0002-1534-2690" }, { "id": "Matier-Carson-D", "name": { "family": "Matier", "given": "Carson D." }, "orcid": "0000-0002-1618-7944" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Enantioconvergent Alkylations of Amines by Alkyl Electrophiles: Copper-Catalyzed Nucleophilic Substitutions of Racemic \u03b1-Halolactams by Indoles", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2019 American Chemical Society. \n\nReceived 23 July 2019. Published online 9 September 2019. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences; Grant No. R01-GM109194), the Bengt Lundqvist Memorial Foundation of the Swedish Chemical Society (fellowship for A.B.), Boehringer\u2013Ingelheim Pharmaceuticals (Scientific Advancement Grant to G.C.F.), and the Dow Next Generation Educator Fund (grant to Caltech). We thank Prof. Jonas C. Peters, Dr. Quirin M. Kainz, Dr. J. M. Ahn, Lawrence M. Henling, Dr. Nathan D. Schley, Dr. Mona Shahgholi, Dr. Michael K. Takase, Dr. Scott C. Virgil, and Dr. Susan L. Zultanski for assistance and helpful discussions. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms-1557306.pdf
Supplemental Material - ja9b07875_si_001.pdf
", "abstract": "Transition-metal catalysis has the potential to address shortcomings in the classic S_N2 reaction of an amine with an alkyl electrophile, both with respect to reactivity and to enantioselectivity. In this study, we describe the development of a user-friendly method (reaction at room temperature, with commercially available catalyst components) for the enantioconvergent nucleophilic substitution of racemic secondary alkyl halides (\u03b1-iodolactams) by indoles. Mechanistic studies are consistent with the formation of a copper(I)\u2013indolyl complex that reacts at different rates with the two enantiomers of the electrophile, which interconvert under the reaction conditions (dynamic kinetic resolution). This investigation complements earlier work on photoinduced enantioconvergent N-alkylation, supporting the premise that this important challenge can be addressed by a range of strategies.", "date": "2019-09-18", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "141", "number": "37", "publisher": "American Chemical Society", "pagerange": "14864-14869", "id_number": "CaltechAUTHORS:20190909-093503148", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20190909-093503148", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM109194" }, { "agency": "Bengt Lundqvists Minnesfond" }, { "agency": "Swedish Chemical Society" }, { "agency": "Boehringer Ingelheim" }, { "agency": "Dow Next Generation Educator Fund" } ] }, "doi": "10.1021/jacs.9b07875", "pmcid": "PMC7055584", "primary_object": { "basename": "nihms-1557306.pdf", "url": "https://authors.library.caltech.edu/records/s7gby-4k828/files/nihms-1557306.pdf" }, "related_objects": [ { "basename": "ja9b07875_si_001.pdf", "url": "https://authors.library.caltech.edu/records/s7gby-4k828/files/ja9b07875_si_001.pdf" } ], "resource_type": "article", "pub_year": "2019", "author_list": "Bartoszewicz, Agnieszka; Matier, Carson D.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/5ph31-dg850", "eprint_id": 101187, "eprint_status": "archive", "datestamp": "2023-08-19 16:48:30", "lastmod": "2023-10-20 22:03:05", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Masuda-Yusuke", "name": { "family": "Masuda", "given": "Yusuke" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Synthesis of Chiral Diamine Ligands for Nickel-catalyzed Asymmetric Cross-couplings of Alkylchloroboronate Esters with Alkylzincs: (1R,2R)-N,N'-Dimethyl-1,2-bis(2-methylphenyl)-1,2-diaminoethane", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2019 Organic Syntheses, Inc. \n\nChecked by Skyler Mendoza and Sarah E. Reisman. \n\nPublished on the Web 7/19/2019.\n\nPublished - v96p0245.pdf
Accepted Version - nihms-1566744.pdf
", "abstract": "A. (1R,2R)-N,N'-Bis(2-hydroxyphenylmethylene)-1,2-bis(2-methylphenyl)-1,2-diaminoethane (1). An oven-dried, 100-mL, two-necked, round-bottomed flask equipped with a magnetic stir bar (13 \u00d7 9 mm, octagon-type), a rubber septum, and a nitrogen line is evacuated under high vacuum (1.0 mmHg) and filled with nitrogen (three cycles). (1S,2S)-1,2-Bis(2-hydroxyphenyl)-1,2-diaminoethane (1.0 g, 4.1 mmol, 1.0 equiv) (Note 2) is added through the open neck under a positive pressure of nitrogen. The open neck is capped with a rubber septum, and then anhydrous DMSO (20 mL) (Note 3) and 2-methylbenzaldehyde (1.23 g, 10.2 mmol, 2.5 equiv) (Note 4) are added into the flask by syringe through the rubber septum. After the yellow solution (Figure 1) is stirred for 14 h at 20 \u00b0C, the reaction is quenched by the addition of distilled water (100 mL), and the mixture is extracted with Et\u2082O (20 mL \u00d7 3). The combined organic layer is washed with water (30 mL) and a saturated aqueous solution of NaCl (30 mL), dried over anhydrous Na\u2082SO\u2084 (5 g), filtered through filter paper, and concentrated by rotary evaporation (30 mmHg, 30 \u00b0C) and under vacuum (1.0 mmHg). The product, obtained as a yellow oil as a mixture with unreacted 2-methylbenzaldehyde, is used in the next step without further purification (2.2 g, ~98% yield) (Note 5).", "date": "2019-07-17", "date_type": "published", "publication": "Organic Syntheses", "volume": "96", "publisher": "Organic Syntheses, Inc.", "pagerange": "245-257", "id_number": "CaltechAUTHORS:20200210-082805136", "issn": "2333-3553", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200210-082805136", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "doi": "10.15227/orgsyn.096.0245", "pmcid": "PMC7064032", "primary_object": { "basename": "nihms-1566744.pdf", "url": "https://authors.library.caltech.edu/records/5ph31-dg850/files/nihms-1566744.pdf" }, "related_objects": [ { "basename": "v96p0245.pdf", "url": "https://authors.library.caltech.edu/records/5ph31-dg850/files/v96p0245.pdf" } ], "resource_type": "article", "pub_year": "2019", "author_list": "Masuda, Yusuke and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/tn7tr-6dy56", "eprint_id": 93900, "eprint_status": "archive", "datestamp": "2023-08-19 15:06:40", "lastmod": "2023-10-20 17:30:22", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory Chung-Wei" }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Nucleophilic substitution reactions: A radical alternative to SN_1 and SN_2 reactions", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2019 American Chemical Society.", "abstract": "Classical methods for achieving nucleophilic substitutions of alkyl electrophiles (SN_1 and SN_2) have limited scope and are not generally amenable to enantioselective variants that employ readily available racemic electrophiles. In this\npresentation, we will describe how the combination of radical chem. and transition-metal catalysis has opened the door to addressing the challenges of reactivity and of enantioselectivity in nucleophilic substitution reactions of secondary and tertiary alkyl electrophiles.", "date": "2019-04", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20190318-073543823", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20190318-073543823", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "resource_type": "conference_item", "pub_year": "2019", "author_list": "Fu, Gregory Chung-Wei" }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/yd105-jez89", "eprint_id": 92389, "eprint_status": "archive", "datestamp": "2023-08-22 01:07:11", "lastmod": "2023-10-20 00:14:41", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Enantioconvergent Cross\u2212Couplings of Alkyl Electrophiles: The Catalytic Asymmetric Synthesis of Organosilanes", "ispublished": "pub", "full_text_status": "public", "keywords": "alkylation; asymmetric catalysis; cross-coupling; nickel; silicon", "note": "\u00a9 2019 Wiley\u2010VCH Verlag GmbH & Co. KGaA, Weinheim. \n\nManuscript received: December 13, 2018; Accepted manuscript online: January 16, 2019; Version of record online: February 5, 2019. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences; grant R01\u2013GM062871 to G.C.F. and grant F32\u2013GM116234 to G.M.S.) and the Dow Next Generation Educator Fund (grant to Caltech). We thank Dr. Jun Myun Ahn, Dr. Paul H. Oyala (Caltech EPR Facility), Dr. Mona Shahgholi (Caltech Mass Spectrometry Facility), Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis), Dr. Haolin Yin, and Wanji Zhang for assistance and helpful discussions. \n\nThe authors declare no conflict of interest.\n\nAccepted Version - Fu-2019-Angewandte_Chemie_International_Edition.pdf
Accepted Version - nihms-1008170.pdf
Supplemental Material - anie201814208-s1-supporting_information.pdf
", "abstract": "Metal\u2010catalyzed enantioconvergent cross\u2010coupling reactions of alkyl electrophiles are emerging as a powerful tool in asymmetric synthesis. To date, high enantioselectivity has been limited to couplings of electrophiles that bear a directing group or a proximal p/\u03c0 orbital. Herein, we demonstrate for the first time that enantioconvergent cross\u2010couplings can be achieved with electrophiles that lack such features; specifically, we establish that a chiral nickel catalyst can accomplish Negishi reactions of racemic \u03b1\u2010halosilanes with alkylzinc reagents with good enantioselectivity under simple and mild conditions, thereby providing access to enantioenriched organosilanes, an important class of target molecules.", "date": "2019-03-11", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "58", "number": "11", "publisher": "Wiley", "pagerange": "3571-3574", "id_number": "CaltechAUTHORS:20190122-084528318", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20190122-084528318", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01 GM062871" }, { "agency": "NIH Postdoctoral Fellowship", "grant_number": "F32 GM116234" }, { "agency": "Dow Next Generation Educator Fund" } ] }, "doi": "10.1002/anie.201814208", "pmcid": "PMC6399024", "primary_object": { "basename": "Fu-2019-Angewandte_Chemie_International_Edition.pdf", "url": "https://authors.library.caltech.edu/records/yd105-jez89/files/Fu-2019-Angewandte_Chemie_International_Edition.pdf" }, "related_objects": [ { "basename": "anie201814208-s1-supporting_information.pdf", "url": "https://authors.library.caltech.edu/records/yd105-jez89/files/anie201814208-s1-supporting_information.pdf" }, { "basename": "nihms-1008170.pdf", "url": "https://authors.library.caltech.edu/records/yd105-jez89/files/nihms-1008170.pdf" } ], "resource_type": "article", "pub_year": "2019", "author_list": "Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/gsbbf-7p433", "eprint_id": 90547, "eprint_status": "archive", "datestamp": "2023-08-19 13:11:42", "lastmod": "2023-10-18 23:31:20", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "He-Jian", "name": { "family": "He", "given": "Jian" }, "orcid": "0000-0002-3388-3239" }, { "id": "Chen-Caiyou", "name": { "family": "Chen", "given": "Caiyou" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Visible-Light-Induced, Copper-Catalyzed Three-Component Coupling of Alkyl Halides, Olefins, and Trifluoromethylthiolate to Generate Trifluoromethyl Thioethers", "ispublished": "pub", "full_text_status": "public", "keywords": "copper catalysis, C\u2013S bond formation, three-component cross-coupling, photoredox catalysis, photochemistry", "note": "\u00a9 2018 American Chemical Society. \n\nReceived: October 10, 2018; Revised: October 24, 2018; Published: October 31, 2018. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-109194). We are also grateful to the Dow Next Generation Educator Fund. We thank Dr. Tanvi S. Ratani, Dr. Paul H. Oyala (Caltech EPR Facility, supported by NSF-1531940), Larry M. Henling, Dr. Jun Myun Ahn, and Theodore M. Donnell for experimental assistance and for helpful discussions. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms-1011573.pdf
Supplemental Material - cs8b04094_si_001.pdf
Supplemental Material - cs8b04094_si_002.cif
", "abstract": "Photoinduced, copper-catalyzed coupling reactions are emerging as a powerful method for generating Csp^3\u2013Y (Y = C or heteroatom) bonds from alkyl electrophiles and nucleophiles. Corresponding three-component couplings of alkyl electrophiles, olefins, and nucleophiles have the potential to generate an additional Csp3\u2013Y bond and to efficiently add functional groups to both carbons of an olefin, which serves as a readily available linchpin. In this report, we establish that a variety of electrophiles and a trifluoromethylthiolate nucleophile can add across an array of olefins (including styrenes and electron-poor olefins) in the presence of CuI/binap and blue-LED irradiation, thereby generating trifluoromethyl thioethers in good yield. The process tolerates a wide range of functional groups, and an initial survey of other nucleophiles (i.e., bromide, cyanide, and azide) suggests that this three-component coupling strategy is versatile. Mechanistic studies are consistent with a photoexcited Cu(I)/binap/SCF_3 complex serving as a reductant to generate an alkyl radical from the electrophile, which likely reacts in turn with the olefin and a Cu(II)/SCF_3 complex to afford the coupling product.", "date": "2018-12-07", "date_type": "published", "publication": "ACS Catalysis", "volume": "8", "number": "12", "publisher": "American Chemical Society", "pagerange": "11741-11748", "id_number": "CaltechAUTHORS:20181031-131746669", "issn": "2155-5435", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20181031-131746669", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-109194" }, { "agency": "NSF", "grant_number": "CHE-1531940" } ] }, "doi": "10.1021/acscatal.8b04094", "pmcid": "PMC6687088", "primary_object": { "basename": "cs8b04094_si_001.pdf", "url": "https://authors.library.caltech.edu/records/gsbbf-7p433/files/cs8b04094_si_001.pdf" }, "related_objects": [ { "basename": "cs8b04094_si_002.cif", "url": "https://authors.library.caltech.edu/records/gsbbf-7p433/files/cs8b04094_si_002.cif" }, { "basename": "nihms-1011573.pdf", "url": "https://authors.library.caltech.edu/records/gsbbf-7p433/files/nihms-1011573.pdf" } ], "resource_type": "article", "pub_year": "2018", "author_list": "He, Jian; Chen, Caiyou; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/428ka-b6y61", "eprint_id": 90086, "eprint_status": "archive", "datestamp": "2023-08-19 12:44:19", "lastmod": "2023-10-18 23:11:25", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Wang-Zhaobin", "name": { "family": "Wang", "given": "Zhaobin" } }, { "id": "Yin-Haolin", "name": { "family": "Yin", "given": "Haolin" }, "orcid": "0000-0002-2063-8605" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Catalytic Enantioconvergent Couplings of Secondary and Tertiary Electrophiles with Olefins", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2018 Springer Nature Limited. \n\nReceived 30 April 2018; Accepted 11 October 2018; Published\n18 October 2018. \n\nData availability: The data that support the findings of this study are available within the paper, its Supplementary Information (experimental procedures and characterization data) and from the Cambridge Crystallographic Data Centre (https://www.ccdc.cam.ac.uk/structures; crystallographic data are available free of charge under CCDC reference numbers 1822790\u20131822793, 1839344\u20131839346 and 1861568). \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, R01\u2013GM62871) and the Gordon and Betty Moore Foundation (Caltech Center for Catalysis and Chemical Synthesis). We thank L. M. Henling, D. G. VanderVelde and S. C. Virgil for assistance and discussions. \n\nAuthor Contributions: Z.W. and H.Y. performed all experiments. Z.W. and G.C.F. wrote the manuscript. All authors contributed to the analysis and the interpretation of the results. \n\nThe authors declare no competing interests.\n\nAccepted Version - nihms-1509552.pdf
Supplemental Material - 41586_2018_669_MOESM1_ESM.pdf
Supplemental Material - 41586_2018_669_MOESM2_ESM.zip
", "abstract": "Carbon\u2013carbon bonds, including those between sp^3-hybridized carbon atoms (alkyl\u2013alkyl bonds), typically comprise much of the framework of organic molecules. In the case of s^p3-hybridized carbon, the carbon can be stereogenic and the particular stereochemistry can have implications for structure and function. As a consequence, the development of methods that simultaneously construct alkyl\u2013alkyl bonds and control stereochemistry is important, although challenging. Here we describe a strategy for enantioselective alkyl\u2013alkyl bond formation, in which a racemic alkyl electrophile is coupled with an olefin in the presence of a hydrosilane, through the action of a chiral nickel catalyst. We demonstrate that families of racemic alkyl halides\u2014including secondary and tertiary electrophiles, which have not previously been shown to be suitable for enantioconvergent coupling with alkyl metal nucleophiles\u2014cross-couple with olefins with good enantioselectivity and yield under very mild reaction conditions. Given the ready availability of olefins, our approach opens the door to developing more general methods for enantioconvergent alkyl\u2013alkyl coupling.", "date": "2018-11-15", "date_type": "published", "publication": "Nature", "volume": "563", "number": "7731", "publisher": "Nature Publishing Group", "pagerange": "379-383", "id_number": "CaltechAUTHORS:20181002-161720440", "issn": "0028-0836", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20181002-161720440", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1038/s41586-018-0669-y", "pmcid": "PMC6296363", "primary_object": { "basename": "41586_2018_669_MOESM2_ESM.zip", "url": "https://authors.library.caltech.edu/records/428ka-b6y61/files/41586_2018_669_MOESM2_ESM.zip" }, "related_objects": [ { "basename": "nihms-1509552.pdf", "url": "https://authors.library.caltech.edu/records/428ka-b6y61/files/nihms-1509552.pdf" }, { "basename": "41586_2018_669_MOESM1_ESM.pdf", "url": "https://authors.library.caltech.edu/records/428ka-b6y61/files/41586_2018_669_MOESM1_ESM.pdf" } ], "resource_type": "article", "pub_year": "2018", "author_list": "Wang, Zhaobin; Yin, Haolin; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/tavbk-74s42", "eprint_id": 88606, "eprint_status": "archive", "datestamp": "2023-09-22 22:47:49", "lastmod": "2023-10-23 23:28:59", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Wang-Zhaobin", "name": { "family": "Wang", "given": "Zhaobin" } }, { "id": "Bachman-S", "name": { "family": "Bachman", "given": "Shoshana" } }, { "id": "Dudnik-A-S", "name": { "family": "Dudnik", "given": "Alexander S." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Nickel-Catalyzed Enantioconvergent Borylation of Racemic Secondary Benzylic Electrophiles", "ispublished": "pub", "full_text_status": "public", "keywords": "asymmetric catalysis \u2022 boron \u2022 cross-coupling \u2022 nickel", "note": "\u00a9 2018 John Wiley & Sons. \n\nManuscript received: May 24, 2018; Revised manuscript received: July 10, 2018; Accepted manuscript online: August 5, 2018; Version of record online: August 19, 2018. \n\nSpecial Issue: 150th Anniversary of the Technical University of Munich. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, grant R01-GM062871). We thank Dr. Scott C. Virgil, Dr. David G. VanderVelde, Dr. Xin Mu, and Dr. Yufan Liang for assistance and helpful discussions. \n\nThe authors declare no conflict of interest.\n\nAccepted Version - Fu_et_al-2018-Angewandte_Chemie_International_Edition.pdf
Accepted Version - nihms-992563.pdf
Supplemental Material - anie201806015-s1-sifor_publicationsupporting_information.pdf
", "abstract": "Nickel\u2010catalyzed cross\u2010coupling has emerged as the most versatile approach to date for achieving enantioconvergent carbon\u2013carbon bond formation using racemic alkyl halides as electrophiles. In contrast, there have not yet been reports of the application of chiral nickel catalysts to the corresponding reactions with heteroatom nucleophiles to produce carbon\u2013heteroatom bonds with good enantioselectivity. Herein, we establish that a chiral nickel/pybox catalyst can borylate racemic secondary benzylic chlorides to provide enantioenriched benzylic boronic esters, a highly useful family of compounds in organic synthesis. The method displays good functional group compatibility (e.g., being unimpeded by the presence of an indole, a ketone, a tertiary amine, or an unactivated alkyl bromide), and both of the catalyst components (NiCl_2\u22c5glyme and the pybox ligand) are commercially available.", "date": "2018-10-26", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "57", "number": "44", "publisher": "Wiley", "pagerange": "14529-14532", "id_number": "CaltechAUTHORS:20180806-125754691", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180806-125754691", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM062871" } ] }, "doi": "10.1002/anie.201806015", "pmcid": "PMC6200647", "primary_object": { "basename": "Fu_et_al-2018-Angewandte_Chemie_International_Edition.pdf", "url": "https://authors.library.caltech.edu/records/tavbk-74s42/files/Fu_et_al-2018-Angewandte_Chemie_International_Edition.pdf" }, "related_objects": [ { "basename": "anie201806015-s1-sifor_publicationsupporting_information.pdf", "url": "https://authors.library.caltech.edu/records/tavbk-74s42/files/anie201806015-s1-sifor_publicationsupporting_information.pdf" }, { "basename": "nihms-992563.pdf", "url": "https://authors.library.caltech.edu/records/tavbk-74s42/files/nihms-992563.pdf" } ], "resource_type": "article", "pub_year": "2018", "author_list": "Wang, Zhaobin; Bachman, Shoshana; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/w8vbn-5q735", "eprint_id": 85845, "eprint_status": "archive", "datestamp": "2023-08-19 08:05:16", "lastmod": "2023-10-18 18:51:58", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Award Address (Herbert C. Brown Award for Creative Research in Synthetic Methods sponsored by the Purdue Borane Research Fund and the Herbert C. Brown Award Endowment). Nucleophilic substitution reactions: A radical alternative to S_N1 and S_N2 reactions", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2018 American Chemical Society.", "abstract": "Classical methods for achieving nucleophilic substitutions of alkyl electrophiles (S_N1 and S_N2) have limited scope and are not\ngenerally amenable to enantioselective variants that employ readily available racemic electrophiles. In this presentation, we will\ndescribe how the combination of radical chem. and transition-metal catalysis has opened the door to addressing the challenges\nof reactivity and of enantioselectivity in nucleophilic substitution reactions of secondary and tertiary alkyl electrophiles.", "date": "2018-03", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20180413-142635264", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180413-142635264", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "resource_type": "conference_item", "pub_year": "2018", "author_list": "Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/gp374-xgt04", "eprint_id": 83538, "eprint_status": "archive", "datestamp": "2023-08-19 06:51:07", "lastmod": "2023-10-17 23:12:49", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Matier-Carson-D", "name": { "family": "Matier", "given": "Carson D." }, "orcid": "0000-0002-1618-7944" }, { "id": "Schwaben-Jonas", "name": { "family": "Schwaben", "given": "Jonas" } }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Copper-Catalyzed Alkylation of Aliphatic Amines Induced by Visible Light", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2017 American Chemical Society. \n\nReceived: September 7, 2017; Published: November 28, 2017. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, grant R01-GM109194) and the Alexander von Humboldt Foundation (fellowship for J.S.). We thank Jun Myun Ahn, Bradley J. Gorsline, Dr. Paul H. Oyala (Caltech EPR Facility, supported by National Science Foundation grant NSF-1531940), Dr. Mona Shahgholi (Caltech Mass Spectrometry Facility), Dr. Yichen Tan, Dr. David G. VanderVelde (Caltech NMR Facility), and Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis) for assistance and helpful discussions. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms-978051.pdf
Supplemental Material - ja7b09582_si_001.pdf
", "abstract": "Although the alkylation of an amine by an alkyl halide serves as a \"textbook example\" of a nucleophilic substitution reaction, the selective mono-alkylation of aliphatic amines by unactivated, hindered halides persists as a largely unsolved challenge in organic synthesis. We report herein that primary aliphatic amines can be cleanly mono-alkylated by unactivated secondary alkyl iodides in the presence of visible light and a copper catalyst. The method operates under mild conditions (\u201310 \u00b0C), displays good functional-group compatibility, and employs commercially available catalyst components. A trapping experiment with TEMPO is consistent with C\u2013N bond formation via an alkyl radical in an out-of-cage process.", "date": "2017-12-13", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "139", "number": "49", "publisher": "American Chemical Society", "pagerange": "17707-17710", "id_number": "CaltechAUTHORS:20171128-135738544", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20171128-135738544", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM109194" }, { "agency": "Alexander von Humboldt Foundation" }, { "agency": "NSF", "grant_number": "CHE-1531940" } ] }, "doi": "10.1021/jacs.7b09582", "pmcid": "PMC6044445", "primary_object": { "basename": "ja7b09582_si_001.pdf", "url": "https://authors.library.caltech.edu/records/gp374-xgt04/files/ja7b09582_si_001.pdf" }, "related_objects": [ { "basename": "nihms-978051.pdf", "url": "https://authors.library.caltech.edu/records/gp374-xgt04/files/nihms-978051.pdf" } ], "resource_type": "article", "pub_year": "2017", "author_list": "Matier, Carson D.; Schwaben, Jonas; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/h774d-a5p24", "eprint_id": 83684, "eprint_status": "archive", "datestamp": "2023-08-19 06:51:18", "lastmod": "2023-10-17 23:24:40", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Ahn-Jun-Myun", "name": { "family": "Ahn", "given": "Jun Myun" }, "orcid": "0000-0002-8181-908X" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Design of a Photoredox Catalyst that Enables the Direct Synthesis of Carbamate-Protected Primary Amines via Photoinduced, Copper-Catalyzed N-Alkylation Reactions of Unactivated Secondary Halides", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2017 American Chemical Society. \n\nReceived: October 12, 2017; Published: December 4, 2017. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, grant R01-GM109194), the Natural Sciences and Engineering Research Council of Canada (graduate research fellowship for J.M.A.), the National Science Foundation (support of the Caltech EPR Facility (NSF-1531940)), and the Arnold and Mabel Beckman Foundation (support of the Beckman Institute Laser Resource Center). We thank Kareem I. Hannoun, Lawrence M. Henling, Dr. Brian C. Sanders, Dr. Jonas Schwaben, Dr. Michael K. Takase, and Dr. Haolin Yin for assistance and helpful discussions. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms978053.pdf
Supplemental Material - ja7b10907_si_001.pdf
", "abstract": "Despite the long history of S_N2 reactions between nitrogen nucleophiles and alkyl electrophiles, many such substitution reactions remain out of reach. In recent years, efforts to develop transition-metal catalysts to address this deficiency have begun to emerge. In this report, we address the challenge of coupling a carbamate nucleophile with an unactivated secondary alkyl electrophile to generate a substituted carbamate, a process that has not been achieved effectively in the absence of a catalyst; the product carbamates can serve as useful intermediates in organic synthesis as well as bioactive compounds in their own right. Through the design and synthesis of a new copper-based photoredox catalyst, bearing a tridentate carbazolide/bisphosphine ligand, that can be activated upon irradiation by blue-LED lamps, we can achieve the coupling of a range of primary carbamates with unactivated secondary alkyl bromides at room temperature. Our mechanistic observations are consistent with the new copper complex serving its intended role as a photoredox catalyst, working in conjunction with a second copper complex that mediates C\u2013N bond formation in an out-of-cage process.", "date": "2017-12-13", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "139", "number": "49", "publisher": "American Chemical Society", "pagerange": "18101-18106", "id_number": "CaltechAUTHORS:20171205-074829551", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20171205-074829551", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM109194" }, { "agency": "Natural Sciences and Engineering Research Council of Canada (NSERC)" }, { "agency": "NSF", "grant_number": "CHE-1531940" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "doi": "10.1021/jacs.7b10907", "pmcid": "PMC6039098", "primary_object": { "basename": "ja7b10907_si_001.pdf", "url": "https://authors.library.caltech.edu/records/h774d-a5p24/files/ja7b10907_si_001.pdf" }, "related_objects": [ { "basename": "nihms978053.pdf", "url": "https://authors.library.caltech.edu/records/h774d-a5p24/files/nihms978053.pdf" } ], "resource_type": "article", "pub_year": "2017", "author_list": "Ahn, Jun Myun; Peters, Jonas C.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/dwhrq-ccs55", "eprint_id": 80616, "eprint_status": "archive", "datestamp": "2023-08-19 05:07:05", "lastmod": "2023-10-17 16:33:39", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Ahn-Jun-Myun", "name": { "family": "Ahn", "given": "Jun Myun" } }, { "id": "Ratani-Tanvi-S", "name": { "family": "Ratani", "given": "Tanvi S." } }, { "id": "Hannoun-Kareem-I", "name": { "family": "Hannoun", "given": "Kareem I." }, "orcid": "0000-0003-3176-1104" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Photoinduced, Copper-Catalyzed Alkylation of Amines: A Mechanistic Study of the Cross-Coupling of Carbazole with Alkyl Bromides", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2017 American Chemical Society. \n\nReceived: July 6, 2017; Published: August 17, 2017. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01\u2013109194), the Natural Sciences and Engineering Research Council of Canada (graduate research fellowship for J.M.A.), and the National Science Foundation (support of the Caltech EPR Facility (NSF-1531940) and a graduate research fellowship for T.S.R.). Additional support has been provided by the Arnold and Mabel Beckman Foundation through the Caltech Beckman Institute Laser Resource Center. We thank Dr. Angel J. Di Bilio, Dr. Paul Oyala, Dr. Sidney E. Creutz, Lawrence M. Henling, Dr. Marcin Kalek, Dr. Wesley Sattler, Dr. Oliver S. Shafaat, Dr. Mona Shahgholi, Dr. David VanderVelde, and Dr. Jay R. Winkler for technical assistance and helpful discussions. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms917166.pdf
Supplemental Material - ja7b07052_si_001.pdf
Supplemental Material - ja7b07052_si_002.cif
Supplemental Material - ja7b07052_si_003.mol
", "abstract": "We have recently reported that a variety of couplings of nitrogen, sulfur, oxygen, and carbon nucleophiles with organic halides can be achieved under mild conditions (\u221240 to 30 \u00b0C) through the use of light and a copper catalyst. Insight into the various mechanisms by which these reactions proceed may enhance our understanding of chemical reactivity and facilitate the development of new methods. In this report, we apply an array of tools (EPR, NMR, transient absorption, and UV\u2013vis spectroscopy; ESI\u2013MS; X-ray crystallography; DFT calculations; reactivity, stereochemical, and product studies) to investigate the photoinduced, copper-catalyzed coupling of carbazole with alkyl bromides. Our observations are consistent with pathways wherein both an excited state of the copper(I) carbazolide complex ([Cu^I(carb)_2]^\u2212) and an excited state of the nucleophile (Li(carb)) can serve as photoreductants of the alkyl bromide. The catalytically dominant pathway proceeds from the excited state of Li(carb), generating a carbazyl radical and an alkyl radical. The cross-coupling of these radicals is catalyzed by copper via an out-of-cage mechanism in which [Cu^I(carb)_2]^\u2212 and [Cu^(II)(carb)_3]^\u2212 (carb = carbazolide), both of which have been identified under coupling conditions, are key intermediates, and [Cu^(II)(carb)_3]^\u2212 serves as the persistent radical that is responsible for predominant cross-coupling. This study underscores the versatility of copper(II) complexes in engaging with radical intermediates that are generated by disparate pathways, en route to targeted bond constructions.", "date": "2017-09-13", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "139", "number": "36", "publisher": "American Chemical Society", "pagerange": "12716-12723", "id_number": "CaltechAUTHORS:20170818-105931485", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170818-105931485", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-109194" }, { "agency": "Natural Sciences and Engineering Research Council of Canada (NSERC)" }, { "agency": "NSF", "grant_number": "CHE-1531940" }, { "agency": "NSF Graduate Research Fellowship" }, { "agency": "Arnold and Mabel Beckman Foundation" } ] }, "doi": "10.1021/jacs.7b07052", "pmcid": "PMC5685493", "primary_object": { "basename": "ja7b07052_si_001.pdf", "url": "https://authors.library.caltech.edu/records/dwhrq-ccs55/files/ja7b07052_si_001.pdf" }, "related_objects": [ { "basename": "ja7b07052_si_002.cif", "url": "https://authors.library.caltech.edu/records/dwhrq-ccs55/files/ja7b07052_si_002.cif" }, { "basename": "ja7b07052_si_003.mol", "url": "https://authors.library.caltech.edu/records/dwhrq-ccs55/files/ja7b07052_si_003.mol" }, { "basename": "nihms917166.pdf", "url": "https://authors.library.caltech.edu/records/dwhrq-ccs55/files/nihms917166.pdf" } ], "resource_type": "article", "pub_year": "2017", "author_list": "Ahn, Jun Myun; Ratani, Tanvi S.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/vsnnk-bjy53", "eprint_id": 80847, "eprint_status": "archive", "datestamp": "2023-08-19 05:03:03", "lastmod": "2023-10-17 18:32:02", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Zhao-Wei", "name": { "family": "Zhao", "given": "Wei" }, "orcid": "0000-0002-4441-9722" }, { "id": "Wurz-Ryan-P", "name": { "family": "Wurz", "given": "Ryan P." }, "orcid": "0000-0003-1413-5208" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Photoinduced, Copper-Catalyzed Decarboxylative C\u2013N Coupling to Generate Protected Amines: An Alternative to the Curtius Rearrangement", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2017 American Chemical Society. \n\nReceived: July 19, 2017; Published: August 25, 2017. \n\nSupport has been provided by Amgen and by the National Institutes of Health (NIGMS: R01-109194). We thank Jun Myun Ahn, Dr. Victor J. Cee, Bradley J. Gorsline, Carson D. Matier, Dr. Paul H. Oyala (Caltech EPR facility, supported by NSF-1531940), and Dr. Haolin Yin for assistance and helpful discussions. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms905801.pdf
Supplemental Material - ja7b07546_si_001.pdf
", "abstract": "The Curtius rearrangement is a classic, powerful method for converting carboxylic acids into protected amines, but its widespread use is impeded by safety issues (the need to handle azides). We have developed an alternative to the Curtius rearrangement that employs a copper catalyst in combination with blue-LED irradiation to achieve the decarboxylative coupling of aliphatic carboxylic acid derivatives (specifically, readily available N-hydroxyphthalimide esters) to afford protected amines under mild conditions. This C\u2013N bond-forming process is compatible with a wide array of functional groups, including an alcohol, aldehyde, epoxide, indole, nitroalkane, and sulfide. Control reactions and mechanistic studies are consistent with the hypothesis that copper species are engaged in both the photochemistry and the key bond-forming step, which occurs through out-of-cage coupling of an alkyl radical.", "date": "2017-09-06", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "139", "number": "35", "publisher": "American Chemical Society", "pagerange": "12153-12156", "id_number": "CaltechAUTHORS:20170828-124616088", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170828-124616088", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Amgen" }, { "agency": "NIH", "grant_number": "R01-109194" }, { "agency": "NSF", "grant_number": "CHE-1531940" } ] }, "doi": "10.1021/jacs.7b07546", "pmcid": "PMC5624330", "primary_object": { "basename": "ja7b07546_si_001.pdf", "url": "https://authors.library.caltech.edu/records/vsnnk-bjy53/files/ja7b07546_si_001.pdf" }, "related_objects": [ { "basename": "nihms905801.pdf", "url": "https://authors.library.caltech.edu/records/vsnnk-bjy53/files/nihms905801.pdf" } ], "resource_type": "article", "pub_year": "2017", "author_list": "Zhao, Wei; Wurz, Ryan P.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/713kv-mq863", "eprint_id": 81398, "eprint_status": "archive", "datestamp": "2023-08-19 04:26:53", "lastmod": "2023-10-17 19:49:21", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "Schwarzwalder-G", "name": { "family": "Schwarzwalder", "given": "Gregg" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory" }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Catalytic asymmetric synthesis of alkylsilanes enabled by stereoconvergent nickel-catalyzed cross-coupling", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2017 American Chemical Society.", "abstract": "Over the years, the Fu group has demonstrated enantioconvergent cross-coupling reactions to be powerful\ntools for the synthesis of chiral mols. Most often, racemic secondary alkyl halide electrophiles are coupled with\nachiral nucleophiles to produce tertiary stereogenic centers in high yield and enantiomeric excess. In this talk, I will discuss our recent application of enantioconvergent nickel catalysis towards the prepn. of unactivated chiral alkyl silanes. The scope and limitations of this approach will be discussed, as well as some further applications of the enantioenriched products.", "date": "2017-08", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20170913-083924596", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170913-083924596", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechAUTHORS", "resource_type": "conference_item", "pub_year": "2017", "author_list": "Schwarzwalder, Gregg and Fu, Gregory" }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/h43bf-yyq68", "eprint_id": 78161, "eprint_status": "archive", "datestamp": "2023-08-19 04:13:43", "lastmod": "2023-10-25 23:49:09", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Transition-Metal Catalysis of Nucleophilic Substitution Reactions: A Radical Alternative to S_N1 and S_N2 Processes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2017 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.\n\nReceived 18 May 2017. Published online 12 June 2017. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM062871 and R01-GM109194). All group members past and present, as well as Prof. Jonas C. Peters and his group, are gratefully acknowledged for their contributions to this research program.\n\nThe author declares no competing financial interest.\n\nPublished - acscentsci.7b00212.pdf
", "abstract": "Classical methods for achieving nucleophilic substitutions of alkyl electrophiles (S_N1 and S_N2) have limited scope and are not generally amenable to enantioselective variants that employ readily available racemic electrophiles. Radical-based pathways catalyzed by chiral transition-metal complexes provide an attractive approach to addressing these limitations", "date": "2017-07-26", "date_type": "published", "publication": "ACS Central Science", "volume": "3", "number": "7", "publisher": "American Chemical Society", "pagerange": "692-700", "id_number": "CaltechAUTHORS:20170613-111718684", "issn": "2374-7943", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170613-111718684", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM062871" }, { "agency": "NIH", "grant_number": "R01-GM109194" } ] }, "collection": "CaltechAUTHORS", "doi": "10.1021/acscentsci.7b00212", "pmcid": "PMC5532721", "primary_object": { "basename": "acscentsci.7b00212.pdf", "url": "https://authors.library.caltech.edu/records/h43bf-yyq68/files/acscentsci.7b00212.pdf" }, "resource_type": "article", "pub_year": "2017", "author_list": "Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/8yas9-vs123", "eprint_id": 76704, "eprint_status": "archive", "datestamp": "2023-08-21 21:03:37", "lastmod": "2023-10-25 16:13:55", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Mu-Xin", "name": { "family": "Mu", "given": "Xin" } }, { "id": "Shibata-Yu", "name": { "family": "Shibata", "given": "Yu" } }, { "id": "Makida-Yusuke", "name": { "family": "Makida", "given": "Yusuke" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Control of Vicinal Stereocenters through Nickel-Catalyzed Alkyl-Alkyl Cross-Coupling", "ispublished": "pub", "full_text_status": "public", "keywords": "alkylation; asymmetric synthesis; cross-coupling; nickel; zinc", "note": "\u00a9 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. \n\nManuscript received: March 6, 2017; Final Article published: April 19, 2017. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM62871), the Shanghai Institute of Organic Chemistry (fellowship to X.M.), and the Japan Society for the Promotion of Science (fellowship to Y.M.). We thank Jun Myun Ahn (x-ray crystallography), Lawrence M. Henling (Caltech X-Ray Crystallography Facility), Dr. Nathan Schley (x-ray crystallography), Samantha\u2005E. Shockley (Stoltz lab), Dr. Scott\u2005C. Virgil (Caltech Center for Catalysis and Chemical Synthesis), Dr. David\u2005G. VanderVelde (Caltech NMR facility), and Dr. Haolin Yin for assistance. \n\nThe authors declare no conflict of interest.\n\nAccepted Version - nihms888555.pdf
Supplemental Material - anie201702402-sup-0001-misc_information.pdf
", "abstract": "Vicinal stereocenters are found in many natural and unnatural compounds. Although metal-catalyzed cross-coupling reactions of unactivated alkyl electrophiles are emerging as a powerful tool in organic synthesis, there have been virtually no reports of processes that generate, much less control, vicinal stereocenters. In this investigation, we establish that a chiral nickel catalyst can mediate doubly stereoconvergent alkyl\u2013alkyl cross-coupling, specifically, reactions of a racemic pyrrolidine-derived nucleophile with cyclic alkyl halides (as mixtures of stereoisomers) to produce vicinal stereocenters with very good stereoselectivity.", "date": "2017-05-15", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "56", "number": "21", "publisher": "Wiley", "pagerange": "5821-5824", "id_number": "CaltechAUTHORS:20170419-135029412", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170419-135029412", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Shanghai Institute of Organic Chemistry (SIOC)" }, { "agency": "Japan Society for the Promotion of Science (JSPS)" } ] }, "doi": "10.1002/anie.201702402", "pmcid": "PMC5595219", "primary_object": { "basename": "anie201702402-sup-0001-misc_information.pdf", "url": "https://authors.library.caltech.edu/records/8yas9-vs123/files/anie201702402-sup-0001-misc_information.pdf" }, "related_objects": [ { "basename": "nihms888555.pdf", "url": "https://authors.library.caltech.edu/records/8yas9-vs123/files/nihms888555.pdf" } ], "resource_type": "article", "pub_year": "2017", "author_list": "Mu, Xin; Shibata, Yu; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/7e5k0-27c24", "eprint_id": 76559, "eprint_status": "archive", "datestamp": "2023-08-19 02:36:33", "lastmod": "2023-10-25 16:07:01", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Choi-Junwon", "name": { "family": "Choi", "given": "Junwon" }, "orcid": "0000-0001-6004-5524" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Transition metal\u2013catalyzed alkyl-alkyl bond formation: Another dimension in cross-coupling chemistry", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2017 American Association for the Advancement of Science.\n\nSupported by National Institute of General Medical Sciences grant R01-GM62871.\n\nAccepted Version - nihms905813.pdf
", "abstract": "BACKGROUND: The development of useful new methods for the construction of carbon-carbon bonds has had an impact on the many scientific disciplines (including materials science, biology, and chemistry) that use organic compounds. Tremendous progress has been made in the past several decades in the creation of bonds between sp^2-hybridized carbons (e.g., aryl-aryl bonds), particularly through the use of transition metal catalysis. In contrast, until recently, advances in the development of general methods that form bonds between sp^3-hybridized carbons (alkyl-alkyl bonds) had been rather limited. A variety of approaches, such as classical S_N^2 reactions and transition metal catalysis, typically led to side reactions rather than the desired carbon-carbon bond formation. With transition metal catalysis, the unwanted but often facile \u03b2-hydride elimination of alkylmetal complexes presented a key impediment to efficient cross-coupling of alkyl electrophiles. \n\nIn the case of many alkyl-alkyl bonds, there is an additional challenge beyond construction of the carbon-carbon bond itself: controlling the stereochemistry at one or both carbons of the new bond. It is important to control the stereochemistry of organic molecules because of its influence on properties such as biological activity. \n\nEach of these two challenges is difficult to solve individually; addressing them simultaneously is even more demanding. Until recently, the methods for achieving alkyl-alkyl bond formation were comparatively limited in scope, typically involving the use of unhindered (e.g., primary) electrophiles and unhindered, highly reactive nucleophiles (e.g., Grignard reagents, which have relatively poor functional group compatibility). With respect to enantioconvergent reactions, there were virtually no examples. \n\nADVANCES: In recent years, it has been established that, through the action of an appropriate transition metal catalyst, it is possible to achieve a broad range of alkyl-alkyl bond-forming processes; nickel-based catalysts have proved to be especially effective. With respect to the electrophilic coupling partner, a wide range of secondary alkyl halides are now suitable. This has enabled the development of enantioconvergent reactions of readily available racemic secondary electrophiles. In view of the abundance of tertiary stereocenters in organic molecules, this is a noteworthy advance in synthesis. \n\nWith respect to the nucleophilic partner, alkylboron and alkylzinc reagents (Suzuki- and Negishi-type reactions, respectively) can now be used in a wide variety of alkyl-alkyl couplings, which greatly increases the utility of such processes, as these nucleophiles are more readily available and have much improved functional group compatibility relative to Grignard reagents. These new methods for alkyl-alkyl bond formation have been applied to the synthesis of natural products and other bioactive compounds. \n\nOUTLOOK: A number of major challenges remain. For example, with regard to the electrophilic coupling partner, there is a need to develop general methods that are effective for tertiary alkyl halides, including enantioconvergent processes. With regard to the nucleophilic partner, there is a need to discover more versatile catalysts that can use a wide range of hindered (e.g., secondary and tertiary) alkylmetal reagents, as well as to achieve a broad spectrum of enantioconvergent couplings of racemic nucleophiles. These advances can enable the doubly stereoconvergent coupling of a racemic electrophile with a racemic nucleophile. \n\nThe synthesis of alkyl-alkyl bonds is arguably the most important bond construction in organic synthesis. The ability to achieve this bond formation at will, as well as to control the product stereochemistry, would transform organic synthesis and empower the many scientists who use organic molecules. Recent work has provided evidence that transition metal catalysis can address this exciting challenge.", "date": "2017-04-14", "date_type": "published", "publication": "Science", "volume": "356", "number": "6334", "publisher": "American Association for the Advancement of Science", "pagerange": "Art. No. eaaf7230", "id_number": "CaltechAUTHORS:20170413-145407242", "issn": "0036-8075", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170413-145407242", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" } ] }, "doi": "10.1126/science.aaf7230", "pmcid": "PMC5611817", "primary_object": { "basename": "nihms905813.pdf", "url": "https://authors.library.caltech.edu/records/7e5k0-27c24/files/nihms905813.pdf" }, "resource_type": "article", "pub_year": "2017", "author_list": "Choi, Junwon and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/gf680-cy417", "eprint_id": 77147, "eprint_status": "archive", "datestamp": "2023-08-19 02:20:58", "lastmod": "2023-10-25 21:55:15", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Metal-catalyzed cross-coupling reactions of alkyl electrophiles", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2017 American Chemical Society.", "abstract": "Despite the tremendous accomplishments that have been described in the development of transition metal-catalyzed\ncoupling processes, it is nevertheless true that many significant opportunities remain. For example, to date the overwhelming majority of studies have focused on couplings between two sp -hybridized reaction sites (e.g., an aryl metal with an aryl halide). As of 2001, there were relatively few examples of metal-catalyzed coupling reactions of alkyl electrophiles. During the past decade, we have pursued the discovery of transition metal-based catalysts for coupling activated and unactivated alkyl\nelectrophiles that bear \u03b2 hydrogens. Our recent efforts to develop broadly applicable methods, including enantioselective processes, will be discussed.", "date": "2017-04", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20170503-101947409", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170503-101947409", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "resource_type": "conference_item", "pub_year": "2017", "author_list": "Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/3mw9h-grx75", "eprint_id": 75045, "eprint_status": "archive", "datestamp": "2023-08-19 02:09:09", "lastmod": "2023-10-25 14:41:42", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Kalek-Marcin", "name": { "family": "Kalek", "given": "Marcin" }, "orcid": "0000-0002-1595-9818" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Caution in the Use of Nonlinear Effects as a Mechanistic Tool for Catalytic Enantioconvergent Reactions: Intrinsic Negative Nonlinear Effects in the Absence of Higher-Order Species", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2017 American Chemical Society. \n\nReceived 21 February 2017. Published online 9 March 2017. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM62871), the Swedish Research Council (Grant No.: 350-2012-6645), and the Polish National Science Centre (Grant No.: 2014/15/D/ST5/02579). We thank Dr. David G. VanderVelde (NMR Facility), Dr. Scott C. Virgil (Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation), and Dr. Xu Quan for assistance. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms856952.pdf
Supplemental Material - ja7b01826_si_001.pdf
", "abstract": "Investigation of the dependence of product enantiometric excess (ee) on catalyst ee is a widely used tool to probe the mechanism of an enantioselective reaction; in particular, the observation of a nonlinear relationship is usually interpreted as an indication of the presence of one or more species that contain at least two units of the chiral entity. In this report, we demonstrate that catalytic enantioconvergent reactions can display an intrinsic negative nonlinear effect that originates purely from the kinetic characteristics of certain enantioconvergent processes and is independent of possible aggregation of the chiral entity. Specifically, this intrinsic negative nonlinear effect can arise when there is a kinetic resolution of the racemic starting material, and its magnitude is correlated with the selectivity factor and the conversion; the dependence on conversion provides a ready means to distinguish it from a more conventional nonlinear effect. We support our analysis with experimental data for two distinct enantioconvergent processes, one catalyzed by a chiral phosphine and the other by a chiral Pd/phosphine complex.", "date": "2017-03-22", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "139", "number": "11", "publisher": "American Chemical Society", "pagerange": "4225-4229", "id_number": "CaltechAUTHORS:20170313-071527443", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20170313-071527443", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Swedish Research Council", "grant_number": "350-2012-6645" }, { "agency": "National Science Centre (Poland)", "grant_number": "2014/15/D/ST5/02579" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "collection": "CaltechAUTHORS", "doi": "10.1021/jacs.7b01826", "pmcid": "PMC5486213", "primary_object": { "basename": "ja7b01826_si_001.pdf", "url": "https://authors.library.caltech.edu/records/3mw9h-grx75/files/ja7b01826_si_001.pdf" }, "related_objects": [ { "basename": "nihms856952.pdf", "url": "https://authors.library.caltech.edu/records/3mw9h-grx75/files/nihms856952.pdf" } ], "resource_type": "article", "pub_year": "2017", "author_list": "Kalek, Marcin and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/ky472-j7963", "eprint_id": 72724, "eprint_status": "archive", "datestamp": "2023-08-19 00:30:50", "lastmod": "2023-10-23 22:53:06", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Schmidt-Jens", "name": { "family": "Schmidt", "given": "Jens" } }, { "id": "Choi-Junwon", "name": { "family": "Choi", "given": "Junwon" }, "orcid": "0000-0001-6004-5524" }, { "id": "Liu-Albert-Tianxiang", "name": { "family": "Liu", "given": "Albert Tianxiang" } }, { "id": "Slusarczyk-Martin", "name": { "family": "Slusarczyk", "given": "Martin" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "A general, modular method for the catalytic asymmetric synthesis of alkylboronate esters", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 American Association for the Advancement of Science. \n\n23 August 2016; accepted 3 November 2016. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, R01-GM62871), the Alexander von Humboldt Foundation (fellowship for J.S.), the German National Merit Foundation (fellowship for M.S.), the David S. Koons SURF (Summer Undergraduate Research Fellowship) Endowment (fellowship for A.T.L.), and the Gordon and Betty Moore Foundation (for the Caltech Center for Catalysis and Chemical Synthesis). We thank J. M. Ahn, L. M. Henling, M. K. Takase (Caltech X-Ray Crystallography Facility), N. D. Schley, M. Shahgholi (Caltech Mass Spectrometry Facility), D. G. VanderVelde (Caltech NMR Facility), and S. C. Virgil (Caltech Center for Catalysis and Chemical Synthesis) for assistance and helpful discussions. Experimental procedures and characterization data are provided in the supplementary materials. Crystallographic data are available free of charge from the Cambridge Crystallographic Data Centre under reference CCDC-1512445.\n\nAccepted Version - nihms905812.pdf
Supplemental Material - 07/354.6317.1265.DC1/aai8611-Schmidt-SM.pdf
", "abstract": "Alkylboron compounds are an important family of target molecules, serving as useful intermediates, as well as end points, in fields such as pharmaceutical science and organic chemistry. Facile transformation of carbon-boron bonds into a wide variety of carbon-X bonds (where X is, for example, carbon, nitrogen, oxygen, or a halogen), with stereochemical fidelity, renders the generation of enantioenriched alkylboronate esters a powerful tool in synthesis. Here we report the use of a chiral nickel catalyst to achieve stereoconvergent alkyl-alkyl couplings of readily available racemic \u03b1-haloboronates with organozinc reagents under mild conditions. We demonstrate that this method provides straightforward access to a diverse array of enantioenriched alkylboronate esters, in which boron is bound to a stereogenic carbon, and we highlight the utility of these compounds in synthesis.", "date": "2016-12-10", "date_type": "published", "publication": "Science", "volume": "354", "number": "6317", "publisher": "American Association for the Advancement of Science", "pagerange": "1265-1269", "id_number": "CaltechAUTHORS:20161212-113915733", "issn": "0036-8075", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20161212-113915733", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Alexander von Humboldt Foundation" }, { "agency": "Studienstiftung des deutschen Volkes" }, { "agency": "Caltech Summer Undergraduate Research Fellowship (SURF)" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "collection": "CaltechAUTHORS", "doi": "10.1126/science.aai8611", "pmcid": "PMC5619240", "primary_object": { "basename": "nihms905812.pdf", "url": "https://authors.library.caltech.edu/records/ky472-j7963/files/nihms905812.pdf" }, "resource_type": "article", "pub_year": "2016", "author_list": "Schmidt, Jens; Choi, Junwon; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/7gx2a-t1h11", "eprint_id": 70432, "eprint_status": "archive", "datestamp": "2023-08-20 13:52:39", "lastmod": "2023-10-20 22:57:42", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Ziegler-Daniel-T", "name": { "family": "Ziegler", "given": "Daniel T." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Catalytic Enantioselective Carbon\u2013Oxygen Bond Formation: Phosphine-Catalyzed Synthesis of Benzylic Ethers via the Oxidation of Benzylic C\u2013H Bonds", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 American Chemical Society. \n\nReceived: August 13, 2016; Publication Date (Web): September 12, 2016. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, R01-GM57034 and R01-GM062871). We thank William Reichard, Jun Myun Ahn (X-ray crystallography), and Dr. Michael K. Takase (X-ray crystallography) for assistance. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms819660.pdf
Supplemental Material - ja6b08486_si_001.pdf
Supplemental Material - ja6b08486_si_002.cif
Supplemental Material - ja6b08486_si_003.cif
Supplemental Material - ja6b08486_si_004.cif
", "abstract": "Benzylic alcohols and ethers are common subunits in bioactive molecules, as well as useful intermediates in organic chemistry. In this Communication, we describe a new approach to the enantioselective synthesis of benzylic ethers through the chiral phosphine-catalyzed coupling of two readily available partners, \u03b3-aryl-substituted alkynoates and alcohols, under mild conditions. In this process, the alkynoate partner undergoes an internal redox reaction. Specifically, the benzylic position is oxidized with good enantioselectivity, and the alkyne is reduced to the alkene.", "date": "2016-09-21", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "138", "number": "37", "publisher": "American Chemical Society", "pagerange": "12069-12072", "id_number": "CaltechAUTHORS:20160919-131412998", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160919-131412998", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM57034" }, { "agency": "NIH", "grant_number": "R01-GM062871" } ] }, "doi": "10.1021/jacs.6b08486", "pmcid": "PMC5065328", "primary_object": { "basename": "nihms819660.pdf", "url": "https://authors.library.caltech.edu/records/7gx2a-t1h11/files/nihms819660.pdf" }, "related_objects": [ { "basename": "ja6b08486_si_001.pdf", "url": "https://authors.library.caltech.edu/records/7gx2a-t1h11/files/ja6b08486_si_001.pdf" }, { "basename": "ja6b08486_si_002.cif", "url": "https://authors.library.caltech.edu/records/7gx2a-t1h11/files/ja6b08486_si_002.cif" }, { "basename": "ja6b08486_si_003.cif", "url": "https://authors.library.caltech.edu/records/7gx2a-t1h11/files/ja6b08486_si_003.cif" }, { "basename": "ja6b08486_si_004.cif", "url": "https://authors.library.caltech.edu/records/7gx2a-t1h11/files/ja6b08486_si_004.cif" } ], "resource_type": "article", "pub_year": "2016", "author_list": "Ziegler, Daniel T. and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/b5nc8-jm904", "eprint_id": 67285, "eprint_status": "archive", "datestamp": "2023-08-20 11:43:41", "lastmod": "2023-10-18 21:03:19", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Chu-Crystal-K", "name": { "family": "Chu", "given": "Crystal K." }, "orcid": "0000-0002-7783-2564" }, { "id": "Liang-Yufan", "name": { "family": "Liang", "given": "Yufan" }, "orcid": "0000-0002-0533-2982" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Silicon-Carbon Bond Formation via Nickel-Catalyzed Cross-Coupling of Silicon Nucleophiles with Unactivated Secondary and Tertiary Alkyl Electrophiles", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 American Chemical Society. \n\nReceived: April 4, 2016. Publication Date (Web): May 17, 2016. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, R01-GM62871) and the Gordon and Betty Moore Foundation (Caltech Center for Catalysis and Chemical Synthesis). We thank Dr. Alexander S. Dudnik for preliminary observations and Dr. Junwon Choi for helpful discussions. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms815606.pdf
Supplemental Material - ja6b03465_si_001.pdf
", "abstract": "A wide array of cross-coupling methods for the formation of C\u2013C bonds from unactivated alkyl electrophiles have been described in recent years. In contrast, progress in the development of methods for the construction of C\u2013heteroatom bonds has lagged; for example, there have been no reports of metal-catalyzed cross-couplings of unactivated secondary or tertiary alkyl halides with silicon nucleophiles to form C\u2013Si bonds. In this study, we address this challenge, establishing that a simple, commercially available nickel catalyst (NiBr_2\u00b7diglyme) can achieve couplings of alkyl bromides with nucleophilic silicon reagents under unusually mild conditions (e.g., \u221220 \u00b0C); especially noteworthy is our ability to employ unactivated tertiary alkyl halides as electrophilic coupling partners, which is still relatively uncommon in the field of cross-coupling chemistry. Stereochemical, relative reactivity, and radical-trap studies are consistent with a homolytic pathway for C\u2013X bond cleavage.", "date": "2016-05-25", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "138", "number": "20", "publisher": "American Chemical Society", "pagerange": "6404-6407", "id_number": "CaltechAUTHORS:20160524-081446502", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160524-081446502", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1021/jacs.6b03465", "pmcid": "PMC5031417", "primary_object": { "basename": "ja6b03465_si_001.pdf", "url": "https://authors.library.caltech.edu/records/b5nc8-jm904/files/ja6b03465_si_001.pdf" }, "related_objects": [ { "basename": "nihms815606.pdf", "url": "https://authors.library.caltech.edu/records/b5nc8-jm904/files/nihms815606.pdf" } ], "resource_type": "article", "pub_year": "2016", "author_list": "Chu, Crystal K.; Liang, Yufan; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/3b6sm-fn469", "eprint_id": 65997, "eprint_status": "archive", "datestamp": "2023-08-20 10:36:41", "lastmod": "2023-10-18 17:02:47", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Metal-catalyzed cross-coupling reactions of alkyl electrophiles", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2016 American Chemical Society.", "abstract": "Despite the tremendous accomplishments that have been described in the development of transition metal- catalyzed\ncoupling processes, it is nevertheless true that many significant opportunities remain. For example, to date the overwhelming\nmajority of studies have focused on couplings between two sp - hybridized reaction sites (e.g., an aryl metal with an aryl\nhalide) . As of 2001, there were relatively few examples of metal- catalyzed coupling reactions of alkyl electrophiles.\nDuring the past decade, we have pursued the discovery of transition metal- based catalysts for coupling activated and\nunactivated alkyl electrophiles that bear \u03b2 hydrogens. Our recent efforts to develop broadly applicable methods, including\nenantioselective processes, will be discussed.", "date": "2016-03", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20160407-124341537", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160407-124341537", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "resource_type": "conference_item", "pub_year": "2016", "author_list": "Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/3pfsa-qnt42", "eprint_id": 65627, "eprint_status": "archive", "datestamp": "2023-08-20 10:27:06", "lastmod": "2023-10-18 16:11:57", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Johnson-Miles-W", "name": { "family": "Johnson", "given": "Miles W." } }, { "id": "Hannoun-Kareem-I", "name": { "family": "Hannoun", "given": "Kareem I." }, "orcid": "0000-0003-3176-1104" }, { "id": "Tan-Yichen", "name": { "family": "Tan", "given": "Yichen" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "A mechanistic investigation of the photoinduced, copper-mediated cross-coupling of an aryl thiol with an aryl halide", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 The Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. \n\nReceived 07 Dec 2015, Accepted 16 Feb 2016, First published online 24 Feb 2016. \n\nAll publication charges for this article have been paid for by the Royal Society of Chemistry. \n\nWe thank Jun Myun Ahn, Dr Angel J. Di Bilio, Lawrence M. Henling, Tanvi S. Ratani, Dr David VanderVelde, Dr Jay R. Winkler, and members of the laboratory of Prof. Harry B. Gray for assistance, and we thank the Gordon and Betty Moore Foundation and the NIH (NIGMS: R01 GM109194) for funding. Photophysical studies were conducted at the Beckman Institute Laser Resource Center. M. W. J. would like to acknowledge the National Institute of Health for a Ruth L. Kirschstein National Research Service Award (F32GM116412).\n\nPublished - c5sc04709a.pdf
Supplemental Material - c5sc04709a1_si.pdf
Supplemental Material - c5sc04709a2_si2.mol2
Supplemental Material - c5sc04709a3.cif
", "abstract": "Photoinduced, copper-catalyzed cross-coupling can offer a complementary approach to thermal (non-photoinduced) methods for generating C\u2013X (X = C, N, O, S, etc.) bonds. In this report, we describe the first detailed mechanistic investigation of one of the processes that we have developed, specifically, the (stoichiometric) coupling of a copper\u2013thiolate with an aryl iodide. In particular, we focus on the chemistry of a discrete [Cu^I(SAr)_2]\u2212 complex (Ar = 2,6-dimethylphenyl), applying a range of techniques, including ESI-MS, cyclic voltammetry, transient luminescence spectroscopy, optical spectroscopy, DFT calculations, Stern\u2013Volmer analysis, EPR spectroscopy, actinometry, and reactivity studies. The available data are consistent with the viability of a pathway in which photoexcited [Cu^I(SAr)_2]\u2212* serves as an electron donor to an aryl iodide to afford an aryl radical, which then reacts in cage with the newly generated copper(II)\u2013thiolate to furnish the cross-coupling product in a non-chain process.", "date": "2016-02-24", "date_type": "published", "publication": "Chemical Science", "volume": "7", "publisher": "Royal Society of Chemistry", "pagerange": "4091-4100", "id_number": "CaltechAUTHORS:20160323-130838018", "issn": "2041-6520", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160323-130838018", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "NIH", "grant_number": "R01 GM109194" }, { "agency": "NIH Predoctoral Fellowship", "grant_number": "F32GM116412" }, { "agency": "Royal Society of Chemistry" } ] }, "doi": "10.1039/c5sc04709a", "pmcid": "PMC5201211", "primary_object": { "basename": "c5sc04709a.pdf", "url": "https://authors.library.caltech.edu/records/3pfsa-qnt42/files/c5sc04709a.pdf" }, "related_objects": [ { "basename": "c5sc04709a1_si.pdf", "url": "https://authors.library.caltech.edu/records/3pfsa-qnt42/files/c5sc04709a1_si.pdf" }, { "basename": "c5sc04709a2_si2.mol2", "url": "https://authors.library.caltech.edu/records/3pfsa-qnt42/files/c5sc04709a2_si2.mol2" }, { "basename": "c5sc04709a3.cif", "url": "https://authors.library.caltech.edu/records/3pfsa-qnt42/files/c5sc04709a3.cif" } ], "resource_type": "article", "pub_year": "2016", "author_list": "Johnson, Miles W.; Hannoun, Kareem I.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/7e5ra-rbf09", "eprint_id": 64493, "eprint_status": "archive", "datestamp": "2023-10-25 17:22:39", "lastmod": "2023-10-25 17:22:39", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Kainz-Quinn-M", "name": { "family": "Kainz", "given": "Quirin M." } }, { "id": "Matier-Carson-D", "name": { "family": "Matier", "given": "Carson D." }, "orcid": "0000-0002-1618-7944" }, { "id": "Bartoszewicz-Agnieszka", "name": { "family": "Bartoszewicz", "given": "Agnieszka" }, "orcid": "0000-0002-1534-2690" }, { "id": "Zultanski-Susan-L", "name": { "family": "Zultanski", "given": "Susan L." }, "orcid": "0000-0002-4907-9210" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Asymmetric copper-catalyzed C-N cross-couplings induced by visible light", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 American Association for the Advancement of Science. \n\nReceived 10 November 2015; accepted 7 January 2016. \n\nSupport has been provided by NIH (National Institute of General Medical Sciences, grant R01\u2013GM109194), the Gordon and Betty Moore Foundation, the Alexander von Humboldt Foundation (fellowship for Q.M.K.), and the Bengt Lundqvist Memorial Foundation of the Swedish Chemical Society (fellowship for A.B.). We thank J. M. Ahn, L. M. Henling (Caltech X-Ray Crystallography Facility), M. W. Johnson, N. D. Schley, M. Shahgholi (Caltech Mass Spectrometry Facility), M. K. Takase (Caltech X-Ray Crystallography Facility), N. Torian (Caltech Mass Spectrometry Facility), D. G. VanderVelde (Caltech NMR Facility), and S. C. Virgil (Caltech Center for Catalysis and Chemical Synthesis) for assistance and helpful discussions. Experimental procedures and characterization data are provided in the supplementary materials. Metrical parameters for the structures of compounds 1 to 4 are available free of charge from the Cambridge Crystallographic Data Centre under accession numbers CCDC 1435979, 1435978, 1435977, and 1435980.\n\nAccepted Version - nihms-750523.pdf
Supplemental Material - aad8313-Kainz-SM.pdf
", "abstract": "Despite a well-developed and growing body of work in copper catalysis, the potential of copper to serve as a photocatalyst remains underexplored. Here we describe a photoinduced copper-catalyzed method for coupling readily available racemic tertiary alkyl chloride electrophiles with amines to generate fully substituted stereocenters with high enantioselectivity. The reaction proceeds at \u201340\u00b0C under excitation by a blue light-emitting diode and benefits from the use of a single, Earth-abundant transition metal acting as both the photocatalyst and the source of asymmetric induction. An enantioconvergent mechanism transforms the racemic starting material into a single product enantiomer.", "date": "2016-02-12", "date_type": "published", "publication": "Science", "volume": "351", "number": "6274", "publisher": "American Association for the Advancement of Science", "pagerange": "681-684", "id_number": "CaltechAUTHORS:20160216-092106614", "issn": "0036-8075", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160216-092106614", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM109194" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "Alexander von Humboldt Foundation" }, { "agency": "Swedish Chemical Society" } ] }, "collection": "CaltechAUTHORS", "doi": "10.1126/science.aad8313", "pmcid": "PMC4770572", "primary_object": { "basename": "nihms-750523.pdf", "url": "https://authors.library.caltech.edu/records/7e5ra-rbf09/files/nihms-750523.pdf" }, "related_objects": [ { "basename": "NIHMS750523-supplement-Supplemental_Material.pdf", "url": "https://authors.library.caltech.edu/records/7e5ra-rbf09/files/NIHMS750523-supplement-Supplemental_Material.pdf" } ], "resource_type": "article", "pub_year": "2016", "author_list": "Kainz, Quirin M.; Matier, Carson D.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/d22sy-h9318", "eprint_id": 64492, "eprint_status": "archive", "datestamp": "2023-08-20 10:13:13", "lastmod": "2023-10-17 21:26:55", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Zuo-Zhiwei", "name": { "family": "Zuo", "given": "Zhiwei" } }, { "id": "Cong-Huan", "name": { "family": "Cong", "given": "Huan" } }, { "id": "Li-Wei", "name": { "family": "Li", "given": "Wei" }, "orcid": "0000-0003-2543-2558" }, { "id": "Choi-Junwon", "name": { "family": "Choi", "given": "Junwon" }, "orcid": "0000-0001-6004-5524" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" }, { "id": "MacMillan-D-W-C", "name": { "family": "MacMillan", "given": "David W. C." }, "orcid": "0000-0003-3352-4532" } ] }, "title": "Enantioselective Decarboxylative Arylation of \u03b1-Amino Acids via the Merger of Photoredox and Nickel Catalysis", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2016 American Chemical Society. \n\nReceived: December 19, 2015. Publication Date (Web): February 5, 2016. J. Am. Chem. Soc., Article ASAP. \n\nFinancial support was provided by the NIH (NIGMS R01 GM093213 and R01 GM062871) and by gifts from Merck and Amgen. Z.Z. is grateful for a postdoctoral fellowship from the Shanghai Institute of Organic Chemistry. \n\nZ.Z. and H.C. contributed equally to this work. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms777185.pdf
Supplemental Material - ja5b13211_si_001.cif
Supplemental Material - ja5b13211_si_002.pdf
", "abstract": "An asymmetric decarboxylative C_(sp)^3\u2013C_(sp)^2 cross-coupling has been achieved via the synergistic merger of photoredox and nickel catalysis. This mild, operationally simple protocol transforms a wide variety of naturally abundant \u03b1-amino acids and readily available aryl halides into valuable chiral benzylic amines in high enantiomeric excess, thereby producing motifs found in pharmacologically active agents.", "date": "2016-02-05", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "138", "number": "6", "publisher": "American Chemical Society", "pagerange": "1832-1835", "id_number": "CaltechAUTHORS:20160216-091421574", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160216-091421574", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01 GM093213" }, { "agency": "NIH", "grant_number": "R01 GM062871" }, { "agency": "Shanghai Institute of Organic Chemistry (SIOC)" }, { "agency": "Merck" }, { "agency": "Amgen" } ] }, "doi": "10.1021/jacs.5b13211", "pmcid": "PMC4862596", "primary_object": { "basename": "ja5b13211_si_002.pdf", "url": "https://authors.library.caltech.edu/records/d22sy-h9318/files/ja5b13211_si_002.pdf" }, "related_objects": [ { "basename": "nihms777185.pdf", "url": "https://authors.library.caltech.edu/records/d22sy-h9318/files/nihms777185.pdf" }, { "basename": "ja5b13211_si_001.cif", "url": "https://authors.library.caltech.edu/records/d22sy-h9318/files/ja5b13211_si_001.cif" } ], "resource_type": "article", "pub_year": "2016", "author_list": "Zuo, Zhiwei; Cong, Huan; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/y5ybm-c8a77", "eprint_id": 61560, "eprint_status": "archive", "datestamp": "2023-08-20 09:01:20", "lastmod": "2023-10-25 15:00:33", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Ratani-Tanvi-S", "name": { "family": "Ratani", "given": "Tanvi S." } }, { "id": "Bachman-Shoshana", "name": { "family": "Bachman", "given": "Shoshana" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Photoinduced, Copper-Catalyzed Carbon\u2013Carbon Bond Formation with Alkyl Electrophiles: Cyanation of Unactivated Secondary Alkyl Chlorides at Room Temperature", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2015 American Chemical Society. \n\nReceived: August 10, 2015. Publication Date (Web): October 22, 2015. \n\nWe thank Dr. Junwon Choi, Nathaniel T. Kadunce, Dr. Wesley Sattler, Dr. David VanderVelde, Dr. Scott C. Virgil, Paul Walton, and Dr. Daniel T. Ziegler for experimental assistance and for helpful discussions, and we thank the Gordon and Betty Moore Foundation, the National Science Foundation (graduate research fellowship to T.S.R.), and the NIH (NIGMS: R01 GM109194) for funding. \n\nT.S.R. and S.B. contributed equally to this work. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms-739917.pdf
Supplemental Material - ja5b08452_si_001.pdf
", "abstract": "We have recently reported that, in the presence of light and a copper catalyst, nitrogen nucleophiles such as carbazoles and primary amides undergo C\u2013N coupling with alkyl halides under mild conditions. In the present study, we establish that photoinduced, copper-catalyzed alkylation can also be applied to C\u2013C bond formation, specifically, that the cyanation of unactivated secondary alkyl chlorides can be achieved at room temperature to afford nitriles, an important class of target molecules. Thus, in the presence of an inexpensive copper catalyst (CuI; no ligand coadditive) and a readily available light source (UVC compact fluorescent light bulb), a wide array of alkyl halides undergo cyanation in good yield. Our initial mechanistic studies are consistent with the hypothesis that an excited state of [Cu(CN)_2]^\u2212 may play a role, via single electron transfer, in this process. This investigation provides a rare example of a transition metal-catalyzed cyanation of an alkyl halide, as well as the first illustrations of photoinduced, copper-catalyzed alkylation with either a carbon nucleophile or a secondary alkyl chloride.", "date": "2015-11-04", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "137", "number": "43", "publisher": "American Chemical Society", "pagerange": "13902-13907", "id_number": "CaltechAUTHORS:20151027-113729482", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20151027-113729482", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "NSF Graduate Research Fellowship" }, { "agency": "NIH", "grant_number": "R01 GM109194" } ] }, "doi": "10.1021/jacs.5b08452", "pmcid": "PMC4666296", "primary_object": { "basename": "ja5b08452_si_001.pdf", "url": "https://authors.library.caltech.edu/records/y5ybm-c8a77/files/ja5b08452_si_001.pdf" }, "related_objects": [ { "basename": "nihms-739917.pdf", "url": "https://authors.library.caltech.edu/records/y5ybm-c8a77/files/nihms-739917.pdf" } ], "resource_type": "article", "pub_year": "2015", "author_list": "Ratani, Tanvi S.; Bachman, Shoshana; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/cetsj-nd083", "eprint_id": 64949, "eprint_status": "archive", "datestamp": "2023-08-20 08:56:33", "lastmod": "2023-10-17 22:00:35", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "Ahn-Jun-Myun", "name": { "family": "Ahn", "given": "Jun Myun" } }, { "id": "Hannoun-Kareem-I", "name": { "family": "Hannoun", "given": "Kareem" }, "orcid": "0000-0003-3176-1104" }, { "id": "Ratani-Tanvi-S", "name": { "family": "Ratani", "given": "Tanvi" } }, { "id": "Creutz-Sidney-E", "name": { "family": "Creutz", "given": "Sidney" }, "orcid": "0000-0003-4440-5336" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Mechanistic insights into photo-induced, copper-catalyzed alkylations of amines", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2015 American Chemical Society.", "abstract": "Photoinduced, copper-catalyzed cross-couplings have emerged as an attractive class of lightdriven\ntransformations to construct carbon-nitrogen bonds in recent years. Despite the\nbroadening scope with respect to coupling partners, the understanding of the operating\nmechanisms has been limited to date. Herein, a mechanistic investigation of a photoinduced,\ncopper-catalyzed cross-coupling of amines and alkyl halides, including spectroscopic evidence\nfor a copper intermediate, is presented.", "date": "2015-11", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20160302-081446965", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20160302-081446965", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "resource_type": "conference_item", "pub_year": "2015", "author_list": "Ahn, Jun Myun; Hannoun, Kareem; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/8xktr-m9m89", "eprint_id": 59030, "eprint_status": "archive", "datestamp": "2023-08-20 07:42:39", "lastmod": "2023-10-23 19:59:10", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Liang-Yufan", "name": { "family": "Liang", "given": "Yufan" }, "orcid": "0000-0002-0533-2982" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Stereoconvergent Negishi Arylations of Racemic Secondary Alkyl Electrophiles: Differentiating between a CF_3 and an Alkyl Group", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2015 American Chemical Society. \n\nReceived: May 6, 2015. Published: July 23, 2015. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM62871) and the Gordon and Betty Moore Foundation (Caltech Center for Catalysis and Chemical Synthesis). We thank Dr. Allen G. Oliver (University of Notre Dame) and Dr. Nathan D. Schley for assistance.\n\nAccepted Version - nihms727140.pdf
Supplemental Material - ja5b04725_si_001.cif
Supplemental Material - ja5b04725_si_002.cif
Supplemental Material - ja5b04725_si_003.pdf
", "abstract": "In this report, we establish that a readily available nickel/bis(oxazoline) catalyst accomplishes a wide array of enantioconvergent cross-couplings of arylzinc reagents with CF_3-substituted racemic secondary alkyl halides, a process that necessitates that the chiral catalyst be able to effectively distinguish between a CF_3 and an alkyl group in order to provide good ee. We further demonstrate that this method can be applied without modification to the catalytic asymmetric synthesis of other families of fluorinated organic compounds.", "date": "2015-08-05", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "137", "number": "30", "publisher": "American Chemical Society", "pagerange": "9523-9526", "id_number": "CaltechAUTHORS:20150728-091314884", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150728-091314884", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01- GM62871" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1021/jacs.5b04725", "pmcid": "PMC4610818", "primary_object": { "basename": "ja5b04725_si_002.cif", "url": "https://authors.library.caltech.edu/records/8xktr-m9m89/files/ja5b04725_si_002.cif" }, "related_objects": [ { "basename": "ja5b04725_si_003.pdf", "url": "https://authors.library.caltech.edu/records/8xktr-m9m89/files/ja5b04725_si_003.pdf" }, { "basename": "nihms727140.pdf", "url": "https://authors.library.caltech.edu/records/8xktr-m9m89/files/nihms727140.pdf" }, { "basename": "ja5b04725_si_001.cif", "url": "https://authors.library.caltech.edu/records/8xktr-m9m89/files/ja5b04725_si_001.cif" } ], "resource_type": "article", "pub_year": "2015", "author_list": "Liang, Yufan and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/j3hd7-c1x66", "eprint_id": 59023, "eprint_status": "archive", "datestamp": "2023-08-20 07:24:08", "lastmod": "2023-10-23 19:58:41", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Kalek-Marcin", "name": { "family": "Kalek", "given": "Marcin" }, "orcid": "0000-0002-1595-9818" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Phosphine-Catalyzed Doubly Stereoconvergent \u03b3-Additions of Racemic Heterocycles to Racemic Allenoates: The Catalytic Enantioselective Synthesis of Protected \u03b1,\u03b1-Disubstituted \u03b1-Amino Acid Derivatives", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2015 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.\n\nReceived: May 28, 2015. Publication Date (Web): July 20, 2015. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM57034) and the Swedish Research Council (fellowship for M.K.: Dnr 350-2012-6645). We thank Dr. Nathan D. Schley, Dr. Michael K. Takase (X-ray Crystallography Facility; a Bruker KAPPA APEX II X-ray diffractometer was purchased via NSF CRIF:MU Award CHE-0639094), Dr. David G. VanderVelde (NMR Facility), Dr. Scott C. Virgil (Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation), and Dr. Daniel T. Ziegler for assistance. \n\nThe authors declare no competing financial interest.\n\nPublished - jacs.5b05528.pdf
Supplemental Material - ja5b05528_si_001.cif
Supplemental Material - ja5b05528_si_002.pdf
", "abstract": "Methods have recently been developed for the phosphine-catalyzed asymmetric \u03b3-addition of nucleophiles to readily available allenoates and alkynoates to generate useful \u03b1,\u03b2-unsaturated carbonyl compounds that bear a stereogenic center in either the \u03b3 or the \u03b4 position (but not both) with high stereoselectivity. The utility of this approach would be enhanced considerably if the stereochemistry at both termini of the new bond could be controlled effectively. In this report, we describe the achievement of this objective, specifically, that a chiral phosphepine can catalyze the stereoconvergent \u03b3-addition of a racemic nucleophile to a racemic electrophile; through the choice of an appropriate heterocycle as the nucleophilic partner, this new method enables the synthesis of protected \u03b1,\u03b1-disubstituted \u03b1-amino acid derivatives in good yield, diastereoselectivity, and enantioselectivity.", "date": "2015-07-29", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "137", "number": "29", "publisher": "American Chemical Society", "pagerange": "9438-9442", "id_number": "CaltechAUTHORS:20150728-084201151", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150728-084201151", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM57034" }, { "agency": "Swedish Research Council", "grant_number": "Dnr 350-2012-6645" }, { "agency": "NSF", "grant_number": "CHE-0639094" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1021/jacs.5b05528", "pmcid": "PMC4577964", "primary_object": { "basename": "ja5b05528_si_001.cif", "url": "https://authors.library.caltech.edu/records/j3hd7-c1x66/files/ja5b05528_si_001.cif" }, "related_objects": [ { "basename": "ja5b05528_si_002.pdf", "url": "https://authors.library.caltech.edu/records/j3hd7-c1x66/files/ja5b05528_si_002.pdf" }, { "basename": "jacs.5b05528.pdf", "url": "https://authors.library.caltech.edu/records/j3hd7-c1x66/files/jacs.5b05528.pdf" } ], "resource_type": "article", "pub_year": "2015", "author_list": "Kalek, Marcin and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/7v539-az506", "eprint_id": 58302, "eprint_status": "archive", "datestamp": "2023-08-22 16:02:01", "lastmod": "2023-10-23 19:14:07", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Liang-Yufan", "name": { "family": "Liang", "given": "Yufan" }, "orcid": "0000-0002-0533-2982" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Nickel-Catalyzed Alkyl\u2013Alkyl Cross-Couplings of Fluorinated Secondary Electrophiles: A General Approach to the Synthesis of Compounds having a Perfluoroalkyl Substituent", "ispublished": "pub", "full_text_status": "public", "keywords": "cross-coupling; fluorine; homogeneous catalysis; nickel; zinc", "note": "\u00a9 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. \n\nReceived: April 11, 2015; Revised: May 3, 2015; Article first published online: 12 June 2015. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM62871) and the Gordon and Betty Moore Foundation (Caltech Center for Catalysis and Chemical Synthesis). We thank Dr. Nathan D. Schley for helpful discussions.\n\nAccepted Version - nihms711211.pdf
Supplemental Material - anie_201503297_sm_miscellaneous_information.pdf
", "abstract": "Fluorinated organic molecules are of interest in fields ranging from medicinal chemistry to polymer science. Described herein is a mild, convenient, and versatile method for the synthesis of compounds bearing a perfluoroalkyl group attached to a tertiary carbon atom by using an alkyl\u2013alkyl cross-coupling. A nickel catalyst derived from NiCl_2\u22c5glyme and a pybox ligand achieves the coupling of a wide range of fluorinated alkyl halides with alkylzinc reagents at room temperature. A broad array of functional groups is compatible with the reaction conditions, and highly selective couplings can be achieved on the basis of differing levels of fluorination. A mechanistic investigation has established that the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) inhibits cross-coupling under these conditions and that a TEMPO\u2013electrophile adduct can be isolated.", "date": "2015-07-27", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "54", "number": "31", "publisher": "Wiley", "pagerange": "9047-9051", "id_number": "CaltechAUTHORS:20150617-075445770", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150617-075445770", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1002/anie.201503297", "pmcid": "PMC4521909", "primary_object": { "basename": "anie_201503297_sm_miscellaneous_information.pdf", "url": "https://authors.library.caltech.edu/records/7v539-az506/files/anie_201503297_sm_miscellaneous_information.pdf" }, "related_objects": [ { "basename": "nihms711211.pdf", "url": "https://authors.library.caltech.edu/records/7v539-az506/files/nihms711211.pdf" } ], "resource_type": "article", "pub_year": "2015", "author_list": "Liang, Yufan and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/p50qn-rg281", "eprint_id": 56369, "eprint_status": "archive", "datestamp": "2023-08-20 05:46:44", "lastmod": "2023-10-23 15:21:14", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lee-Sarah-Yunmi", "name": { "family": "Lee", "given": "Sarah Yunmi" }, "orcid": "0000-0003-4531-9392" }, { "id": "Fujiwara-Yuji", "name": { "family": "Fujiwara", "given": "Yuji" } }, { "id": "Nishiguchi-Atsuko", "name": { "family": "Nishiguchi", "given": "Atsuko" } }, { "id": "Kalek-Marcin", "name": { "family": "Kalek", "given": "Marcin" }, "orcid": "0000-0002-1595-9818" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Phosphine-Catalyzed Enantioselective Intramolecular [3+2] Annulations To Generate Fused Ring Systems", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2015 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. \n\nReceived: February 23, 2015. Publication Date (Web): March 27, 2015.\n\nThis work is dedicated to the memory of Gregory P. Harlow. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM57034), Dainippon Sumitomo Pharma Co., Ltd. (fellowship for Y.F.), Takeda Pharmaceutical Co. Ltd. (fellowship for A.N.), and the Swedish Research Council (fellowship for M.K.: Dnr 350-2012-6645). We thank Dr. Nathan D. Schley, Dr. Michael K. Takase (X-ray Crystallography Facility; a Bruker KAPPA APEX II X-ray diffractometer was purchased via NSF CRIF:MU award CHE-0639094), Dr. David G. VanderVelde (NMR Facility), Dr.\nScott C. Virgil (Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation), and Daniel T. Ziegler for assistance and for helpful discussions.\n\nPublished - jacs.5b01985.pdf
Supplemental Material - ja5b01985_si_001.cif
Supplemental Material - ja5b01985_si_002.pdf
", "abstract": "Substantial progress has been described in the development of asymmetric variants of the phosphine-catalyzed intermolecular [3+2] annulation of allenes with alkenes; however, there have not been corresponding advances for the intramolecular process, which can generate a higher level of complexity (an additional ring and stereocenter(s)). In this study, we describe the application of chiral phosphepine catalysts to address this challenge, thereby providing access to useful scaffolds that are found in bioactive compounds, including diquinane and quinolin-2-one derivatives, with very good stereoselectivity. The products of the [3+2] annulation can be readily transformed into structures that are even more stereochemically rich. Mechanistic studies are consistent with \u03b2 addition of the phosphepine to the allene being the turnover-limiting step of the catalytic cycle, followed by a concerted [3+2] cycloaddition to the pendant olefin.", "date": "2015-04-08", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "137", "number": "13", "publisher": "American Chemical Society", "pagerange": "4587-4591", "id_number": "CaltechAUTHORS:20150406-090131028", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150406-090131028", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM57034" }, { "agency": "Dainippon Sumitomo Pharma Co., Ltd." }, { "agency": "Takeda Pharmaceutical Co. Ltd." }, { "agency": "Swedish Research Council", "grant_number": "350-2012-6645" }, { "agency": "NSF", "grant_number": "CHE-0639094" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1021/jacs.5b01985", "pmcid": "PMC4433041", "primary_object": { "basename": "ja5b01985_si_001.cif", "url": "https://authors.library.caltech.edu/records/p50qn-rg281/files/ja5b01985_si_001.cif" }, "related_objects": [ { "basename": "ja5b01985_si_002.pdf", "url": "https://authors.library.caltech.edu/records/p50qn-rg281/files/ja5b01985_si_002.pdf" }, { "basename": "jacs.5b01985.pdf", "url": "https://authors.library.caltech.edu/records/p50qn-rg281/files/jacs.5b01985.pdf" } ], "resource_type": "article", "pub_year": "2015", "author_list": "Lee, Sarah Yunmi; Fujiwara, Yuji; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/3v6qq-cf533", "eprint_id": 55966, "eprint_status": "archive", "datestamp": "2023-08-20 05:31:46", "lastmod": "2023-10-20 23:29:24", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Kramer-S\u00f8ren", "name": { "family": "Kramer", "given": "S\u00f8ren" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Use of a New Spirophosphine To Achieve Catalytic Enantioselective [4 + 1] Annulations of Amines with Allenes To Generate Dihydropyrroles", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2015 American Chemical Society. \n\nReceived: February 23, 2015. Publication Date (Web): March 17, 2015. \n\nThis study is dedicated to Prof. Stephen L. Buchwald, a friend and a mentor, on the occasion of his 60th birthday. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM57034) and the Lundbeck Foundation (postdoctoral fellowship for S.K.). We thank Dr. Nathan D. Schley, Dr. Michael K. Takase (Caltech X-ray Crystallography Facility; a Bruker KAPPA APEX II X-ray diffractometer was purchased via NSF CRIF:MU award CHE-0639094 to Caltech), Dr. David G. VanderVelde (Caltech NMR Facility), Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation), and Dr. Susan L. Zultanski (initial synthesis of phosphine 1) for assistance.\n\nAccepted Version - nihms687862.pdf
Supplemental Material - ja5b01944_si_001.pdf
Supplemental Material - ja5b01944_si_002.cif
", "abstract": "Due in part to the common occurrence of five-membered nitrogen heterocycles in bioactive molecules, the discovery of methods for the enantioselective synthesis of such structures is a useful endeavor. Building on a single example by Tong of a phosphine-catalyzed [4 + 1] annulation of an amine with an allene that furnished an achiral dihydropyrrole in 22% yield, we have developed, with the aid of a new chiral spirophosphine catalyst, a method with increased utility, specifically, improved yield, enhanced scope (the use of \u03b3-substituted allenes), and good ee. The enantioenriched dihydropyrrole products can be transformed into other interesting families of compounds with very good stereoselectivity.", "date": "2015-03-25", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "137", "number": "11", "publisher": "American Chemical Society", "pagerange": "3803-3806", "id_number": "CaltechAUTHORS:20150323-103746266", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150323-103746266", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM57034" }, { "agency": "Lundbeck Foundation" }, { "agency": "NSF", "grant_number": "CHE-0639094" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1021/jacs.5b01944", "pmcid": "PMC4433051", "primary_object": { "basename": "nihms687862.pdf", "url": "https://authors.library.caltech.edu/records/3v6qq-cf533/files/nihms687862.pdf" }, "related_objects": [ { "basename": "ja5b01944_si_001.pdf", "url": "https://authors.library.caltech.edu/records/3v6qq-cf533/files/ja5b01944_si_001.pdf" }, { "basename": "ja5b01944_si_002.cif", "url": "https://authors.library.caltech.edu/records/3v6qq-cf533/files/ja5b01944_si_002.cif" } ], "resource_type": "article", "pub_year": "2015", "author_list": "Kramer, S\u00f8ren and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/r9fw4-0zg75", "eprint_id": 56463, "eprint_status": "archive", "datestamp": "2023-08-20 05:07:05", "lastmod": "2023-10-23 15:26:43", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Metal-catalyzed cross-coupling reactions of alkyl electrophiles", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2015 American Chemical Society.", "abstract": "Despite the tremendous accomplishments that have been described in the development of transition metal-catalyzed\ncoupling processes, it is nevertheless true that many significant opportunities remain. For example,\nto date the overwhelming majority of studies have focused on couplings between two sp2-hybridized reaction\nsites (e.g., an aryl metal with an aryl halide). As of 2001, there were relatively few examples of metalcatalyzed\ncoupling reactions of alkyl electrophiles. During the past decade, we have pursued the\ndiscovery of transition metal-based catalysts for coupling activated and unactivated alkyl electrophiles that\nbear b hydrogens. Our recent efforts to develop broadly applicable methods, including enantioselective\nprocesses, will be discussed.", "date": "2015-03", "date_type": "published", "publisher": "American Chemical Society", "id_number": "CaltechAUTHORS:20150408-081923612", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150408-081923612", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "resource_type": "conference_item", "pub_year": "2015", "author_list": "Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/b1j3f-thc02", "eprint_id": 56888, "eprint_status": "archive", "datestamp": "2023-08-20 05:12:08", "lastmod": "2023-10-23 16:06:18", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Photoinduced, copper-catalyzed coupling reaction", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 2015 American Chemical Society.", "abstract": "The Ullmann reaction to form C- N bonds, first described over a century ago, is now a classic method in org. synthesis. During\nthe time since its discovery, there had been no reports of a photoinduced variant. Instead, copper- mediated and coppercatalyzed\nprocesses have generally been effected with the aid of heat (e.g., at 60- 120 \u00b0 C) . Recently, we have established\nthat a photoinduced Ullmann C- N arylation can proceed at a temp. as low as - 40 \u00b0 C. The reaction of an amine with an alkyl\nhalide is a classic \"textbook\" approach to C- N bond construction. For efficient C- N bond formation, the electrophile should\ngenerally be a good substrate for an S_N2 reaction. A mild, transition metal- catalyzed N- alkylation that proceeds through a\nradical pathway for C- X cleavage has the potential to address important limitations of the classic S_N2 approach. In this lecture,\nrecent efforts to address this challenge will be described.", "date": "2015-03", "date_type": "published", "publication": "Abstracts of Papers of the American Chemical Society", "volume": "249", "publisher": "American Chemical Society", "pagerange": "BMGT-9", "id_number": "CaltechAUTHORS:20150422-145402543", "issn": "0065-7727", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150422-145402543", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "resource_type": "article", "pub_year": "2015", "author_list": "Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/s6m9c-1jy22", "eprint_id": 52121, "eprint_status": "archive", "datestamp": "2023-08-20 03:45:16", "lastmod": "2023-10-18 19:35:17", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Schley-N-D", "name": { "family": "Schley", "given": "Nathan D." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Nickel-Catalyzed Negishi Arylations of Propargylic Bromides: A Mechanistic Investigation", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.\n\nReceived: August 24, 2014; Published: November 17, 2014. \n\nThis work was supported by the National Institute of General Medical Sciences of the National Institutes of Health (R01-GM62871 to G.C.F. and Ruth L. Kirschstein National Research Service Award F32-GM105295 to N.D.S.). We thank Trixia M. Buscagan (preliminary results), Dr. Ivory Hills (preliminary results), Dr. Angel J. Di Bilio (EPR), Lawrence M. Henling (X-ray crystallography), Prof. Jonas C. Peters (discussions and equipment), Dr. Christopher Uyeda (electrochemistry), and Dr. David VanderVelde (NMR). We acknowledge the Gordon and Betty Moore Foundation, the Beckman Institute, and the Sanofi\u2013Aventis Bioengineering Research Program at Caltech for their support of the Molecular Observatory at Caltech. The SSRL is supported by the Department of Energy's Office of Biological and Environmental Research as well as by the National Institutes of Health.\n\nPublished - ja508718m.pdf
Supplemental Material - ja508718m_si_001.cif
Supplemental Material - ja508718m_si_002.pdf
", "abstract": "Although nickel-catalyzed stereoconvergent couplings of racemic alkyl electrophiles are emerging as a powerful tool in organic chemistry, to date there have been no systematic mechanistic studies of such processes. Herein, we examine the pathway for enantioselective Negishi arylations of secondary propargylic bromides, and we provide evidence for an unanticipated radical chain pathway wherein oxidative addition of the C\u2013Br bond occurs through a bimetallic mechanism. In particular, we have crystallographically characterized a diamagnetic arylnickel(II) complex, [(i-Pr-pybox)NiIIPh]BAr^F_4, and furnished support for [(i-Pr-pybox)NiIIPh]^+ being the predominant nickel-containing species formed under the catalyzed conditions as well as a key player in the cross-coupling mechanism. On the other hand, our observations do not require a role for an organonickel(I) intermediate (e.g., (i-Pr-pybox)NiIPh), which has previously been suggested to be an intermediate in nickel-catalyzed cross-couplings, oxidatively adding alkyl electrophiles through a monometallic pathway.", "date": "2014-11-26", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "136", "number": "47", "publisher": "American Chemical Society", "pagerange": "16588-16593", "id_number": "CaltechAUTHORS:20141125-080958357", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20141125-080958357", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "NIH Predoctoral Fellowship", "grant_number": "F32-GM105295" }, { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "Caltech Beckman Institute" }, { "agency": "Sanofi-Aventis Bioengineering Research Program" }, { "agency": "Department of Energy (DOE)" } ] }, "doi": "10.1021/ja508718m", "pmcid": "PMC4277758", "primary_object": { "basename": "ja508718m_si_002.pdf", "url": "https://authors.library.caltech.edu/records/s6m9c-1jy22/files/ja508718m_si_002.pdf" }, "related_objects": [ { "basename": "ja508718m.pdf", "url": "https://authors.library.caltech.edu/records/s6m9c-1jy22/files/ja508718m.pdf" }, { "basename": "ja508718m_si_001.cif", "url": "https://authors.library.caltech.edu/records/s6m9c-1jy22/files/ja508718m_si_001.cif" } ], "resource_type": "article", "pub_year": "2014", "author_list": "Schley, Nathan D. and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/qkat2-9nn86", "eprint_id": 50426, "eprint_status": "archive", "datestamp": "2023-08-20 03:44:55", "lastmod": "2023-10-17 23:48:02", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Ziegler-D-T", "name": { "family": "Ziegler", "given": "Daniel T." } }, { "id": "Riesgo-L", "name": { "family": "Riesgo", "given": "Lorena" } }, { "id": "Ikeda-Takuya", "name": { "family": "Ikeda", "given": "Takuya" } }, { "id": "Fujiwara-Yuji", "name": { "family": "Fujiwara", "given": "Yuji" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Biphenyl-Derived Phosphepines as Chiral Nucleophilic Catalysts: Enantioselective [4+1] Annulations To Form Functionalized Cyclopentenes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 Wiley-VCH Verlag GmbH & Co. \n\nReceived: June 2, 2014. Revised: July 15, 2014. Article first published online: 6 Oct 2014. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM57034), EMD Serono (fellowship support for D.T.Z.), the Spanish MICINN (fellowship support for L.R.), Daiichi Sankyo Co., Ltd (fellowship support for T.I.), and Dainippon Sumitomo Pharma Co., Ltd. (fellowship support for Y.F.). We thank Trixia Buscagan, Dr. S\u00f8ren Kramer, Dr. Allen Oliver (University of Notre Dame), Dr. Nathan D.\nSchley, Dr. Michael K. Takase, Dr. David VanderVelde, Dr. Scott C. Virgil, and Dr. Ashraf Wilsily for assistance and for helpful discussions.\n\nAccepted Version - nihms687855.pdf
Supplemental Material - anie_201405854_sm_miscellaneous_information.pdf
", "abstract": "Because of the frequent occurrence of cyclopentane subunits in bioactive compounds, the development of efficient catalytic asymmetric methods for their synthesis is an important objective. Introduced herein is a new family of chiral nucleophilic catalysts, biphenyl-derived phosphepines, and we apply them to an enantioselective variant of a useful [4+1] annulation. A range of one-carbon coupling partners can be employed, thereby generating cyclopentenes which bear a fully substituted stereocenter [either all-carbon or heteroatom-substituted (sulfur and phosphorus)]. Stereocenters at the other four positions of the cyclopentane ring can also be introduced with good stereoselectivity. An initial mechanistic study indicates that phosphine addition to the electrophilic four-carbon coupling partner is not the turnover-limiting step of the catalytic cycle.", "date": "2014-11-24", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "53", "number": "48", "publisher": "Wiley", "pagerange": "13183-13187", "id_number": "CaltechAUTHORS:20141015-153508295", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20141015-153508295", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM57034" }, { "agency": "EMD Serono" }, { "agency": "MICINN Ministerio de Ciencia e Innovaci\u00f3n (MICINN)" }, { "agency": "Daiichi Sankyo Co., Ltd." }, { "agency": "Dainippon Sumitomo Pharma Co., Ltd." } ] }, "doi": "10.1002/anie.201405854", "pmcid": "PMC4433032", "primary_object": { "basename": "anie_201405854_sm_miscellaneous_information.pdf", "url": "https://authors.library.caltech.edu/records/qkat2-9nn86/files/anie_201405854_sm_miscellaneous_information.pdf" }, "related_objects": [ { "basename": "nihms687855.pdf", "url": "https://authors.library.caltech.edu/records/qkat2-9nn86/files/nihms687855.pdf" } ], "resource_type": "article", "pub_year": "2014", "author_list": "Ziegler, Daniel T.; Riesgo, Lorena; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/tnj36-y1t41", "eprint_id": 48836, "eprint_status": "archive", "datestamp": "2023-08-20 02:37:40", "lastmod": "2023-10-17 20:28:15", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Choi-Junwon", "name": { "family": "Choi", "given": "Junwon" }, "orcid": "0000-0001-6004-5524" }, { "id": "Mart\u00edn-Gago-P", "name": { "family": "Mart\u00edn-Gago", "given": "Pablo" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Stereoconvergent Arylations and Alkenylations of Unactivated Alkyl Electrophiles: Catalytic Enantioselective Synthesis of Secondary Sulfonamides and Sulfones", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 American Chemical Society. ACS AuthorChoice + 12, Open Access on 08/15/2015. \n\nReceived: July 8, 2014; Published: August 15, 2014. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM62871), the Kwanjeong Educational Foundation (fellowship for J.C.), and MICINN (fellowship for P.M.-G.). We thank Dr. Ashraf Wilsily, Dr. Nathan D. Schley, Dr. David VanderVelde (Caltech NMR Facility), and Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation) for assistance and for helpful discussions.\n\nPublished - ja506885s.pdf
Supplemental Material - ja506885s_si_001.cif
Supplemental Material - ja506885s_si_002.pdf
", "abstract": "The development of efficient methods for the generation of enantioenriched sulfonamides and sulfones is an important objective for fields such as organic synthesis and medicinal chemistry; however, there have been relatively few reports of direct catalytic asymmetric approaches to controlling the stereochemistry of the sulfur-bearing carbon of such targets. In this report, we describe nickel-catalyzed stereoconvergent Negishi arylations and alkenylations of racemic \u03b1-bromosulfonamides and -sulfones that furnish the desired cross-coupling product in very good ee and yield for an array of reaction partners. Mechanistic studies are consistent with the generation of a radical intermediate that has a sufficient lifetime to diffuse out of the solvent cage and to cyclize onto a pendant olefin.", "date": "2014-08-27", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "136", "number": "34", "publisher": "American Chemical Society", "pagerange": "12161-12165", "id_number": "CaltechAUTHORS:20140825-090042780", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140825-090042780", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Kwanjeong Educational Foundation" }, { "agency": "Ministerio de Ciencia e Innovaci\u00f3n (MICINN)" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1021/ja506885s", "pmcid": "PMC4151784", "primary_object": { "basename": "ja506885s.pdf", "url": "https://authors.library.caltech.edu/records/tnj36-y1t41/files/ja506885s.pdf" }, "related_objects": [ { "basename": "ja506885s_si_001.cif", "url": "https://authors.library.caltech.edu/records/tnj36-y1t41/files/ja506885s_si_001.cif" }, { "basename": "ja506885s_si_002.pdf", "url": "https://authors.library.caltech.edu/records/tnj36-y1t41/files/ja506885s_si_002.pdf" } ], "resource_type": "article", "pub_year": "2014", "author_list": "Choi, Junwon; Mart\u00edn-Gago, Pablo; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/fzagm-4mb43", "eprint_id": 48375, "eprint_status": "archive", "datestamp": "2023-08-20 02:08:34", "lastmod": "2023-10-17 18:45:44", "type": "conference_item", "metadata_visibility": "show", "creators": { "items": [ { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory" }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Catalytic cross-coupling with copper and light", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2014 American Chemical Society.", "abstract": "Carbon-nitrogen bond-forming reactions of amines with aryl halides to generate arylamines (anilines), mediated by a stoichiometric copper reagent at elevated temp. (>180 \u00b0C), were first described by Ullmann in 1903. Recent advances in catalytic Ullmann-type cross-couplings make these bond-forming processes powerful tools for org. synthesis. In this talk I will describe a recent collaborative effort between the Fu and Peters research groups at Caltech to develop photo-induced, copper-catalyzed C-X cross-couplings (X = N, S, O, C) as a methodolgically simple, mild approach to Ullmann-type bond constructions.", "date": "2014-08", "date_type": "published", "publisher": "Caltech Library", "id_number": "CaltechAUTHORS:20140812-105957073", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140812-105957073", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "resource_type": "conference_item", "pub_year": "2014", "author_list": "Peters, Jonas C. and Fu, Gregory" }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/2vn48-bc087", "eprint_id": 47147, "eprint_status": "archive", "datestamp": "2023-08-20 01:44:58", "lastmod": "2023-10-26 20:21:15", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Tan-Yichen", "name": { "family": "Tan", "given": "Yichen" } }, { "id": "Mu\u00f1oz-Molina-J-M", "name": { "family": "Mu\u00f1oz-Molina", "given": "Jos\u00e9 Mar\u00eda" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Oxygen nucleophiles as reaction partners in photoinduced, copper-catalyzed cross-couplings: O-arylations of phenols at room temperature", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 The Royal Society of Chemistry. \n\nReceived 3rd February 2014; Accepted 17th April 2014. First published online 22 Apr 2014. \n\nThis work was supported by the Gordon and Betty Moore Foundation (grant to J.C.P.) and the Council for International Exchange of Scholars (Fulbright Scholar award to J.M.M.-M.). We thank Daniel T. Ziegler for preliminary studies, Sidney E. Creutz for experimental assistance, and the reviewers for constructive comments.\n\nPublished - c4sc00368c.pdf
Supplemental Material - c4sc00368c1_si.pdf
", "abstract": "Most copper-catalyzed cross-couplings require an elevated reaction temperature. Recently, a photoinduced variant has been developed that enables C\u2013X bond-forming reactions of certain nitrogen and sulfur nucleophiles to proceed under unusually mild conditions (\u221240 \u00b0C to room temperature). In view of the importance of carbon\u2013oxygen bond construction in organic chemistry, the expansion of this photochemical approach to oxygen nucleophiles is an important objective. In this report, we establish that, in the presence of light and an inexpensive copper pre-catalyst (CuI), a wide array of phenols and aryl iodides can be coupled to generate diaryl ethers under mild conditions (room temperature) in the presence of a variety of functional groups. Our studies indicate that a Cu(I)\u2013phenoxide complex is a viable intermediate in photoinduced C\u2013O bond-formation.", "date": "2014-07-01", "date_type": "published", "publication": "Chemical Science", "volume": "5", "number": "7", "publisher": "Royal Society of Chemistry", "pagerange": "2831-2835", "id_number": "CaltechAUTHORS:20140710-132652083", "issn": "2041-6520", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140710-132652083", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "Council for International Exchange of Scholars" } ] }, "doi": "10.1039/c4sc00368c", "primary_object": { "basename": "c4sc00368c.pdf", "url": "https://authors.library.caltech.edu/records/2vn48-bc087/files/c4sc00368c.pdf" }, "related_objects": [ { "basename": "c4sc00368c1_si.pdf", "url": "https://authors.library.caltech.edu/records/2vn48-bc087/files/c4sc00368c1_si.pdf" } ], "resource_type": "article", "pub_year": "2014", "author_list": "Tan, Yichen; Mu\u00f1oz-Molina, Jos\u00e9 Mar\u00eda; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/a9d2k-ddj10", "eprint_id": 46273, "eprint_status": "archive", "datestamp": "2023-08-20 01:24:16", "lastmod": "2023-10-26 19:38:22", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lee-Sarah-Yunmi", "name": { "family": "Lee", "given": "Sarah Yunmi" } }, { "id": "Neufeind-S", "name": { "family": "Neufeind", "given": "Stefan" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Enantioselective Nucleophile-Catalyzed Synthesis of Tertiary Alkyl Fluorides via the \u03b1\u2011Fluorination of Ketenes: Synthetic and Mechanistic Studies", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.\n\nReceived: May 2, 2014. Publication Date (Web): June 12, 2014. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences R01-GM57034) and the Deutsche Forschungsgemeinschaft (fellowship to S.N.). We thank Trixia M. Buscagan, Dr. Nathan D. Schley, Dr. Michael K. Takase (X-ray Crystallography Facility; a Bruker KAPPA APEX II X-ray diffractometer was purchased via NSF CRIF:MU award CHE-0639094 to the California Institute of Technology), Dr. David VanderVelde (NMR Facility), and Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation) for assistance.\n\nPublished - ja5044209.pdf
Supplemental Material - ja5044209_si_001.cif
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Supplemental Material - ja5044209_si_004.pdf
", "abstract": "The catalytic asymmetric synthesis of alkyl fluorides, particularly \u03b1-fluorocarbonyl compounds, has been the focus of substantial effort in recent years. While significant progress has been described in the formation of enantioenriched secondary alkyl fluorides, advances in the generation of tertiary alkyl fluorides have been more limited. Here, we describe a method for the catalytic asymmetric coupling of aryl alkyl ketenes with commercially available N-fluorodibenzenesulfonimide (NFSI) and C_6F_5ONa to furnish tertiary \u03b1-fluoroesters. Mechanistic studies are consistent with the hypothesis that the addition of an external nucleophile (C_6F_5ONa) is critical for turnover, releasing the catalyst (PPY*) from an N-acylated intermediate. The available data can be explained by a reaction pathway wherein the enantioselectivity is determined in the turnover-limiting transfer of fluorine from NFSI to a chiral enolate derived from the addition of PPY* to the ketene. The structure and the reactivity of the product of this proposed elementary step, an \u03b1-fluoro-N-acylpyridinium salt, have been examined.", "date": "2014-06-12", "date_type": "published", "publication": "Journal of the American Chemical Society", "publisher": "American Chemical Society", "id_number": "CaltechAUTHORS:20140616-085001666", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140616-085001666", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH National Institute of General Medical Sciences", "grant_number": "R01-GM57034" }, { "agency": "Deutsche Forschungsgemeinschaft (DFG)" }, { "agency": "NSF CRIF:MU Award", "grant_number": "CHE-0639094" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1021/ja5044209", "pmcid": "PMC4091276", "primary_object": { "basename": "ja5044209_si_002.cif", "url": "https://authors.library.caltech.edu/records/a9d2k-ddj10/files/ja5044209_si_002.cif" }, "related_objects": [ { "basename": "ja5044209_si_003.cif", "url": "https://authors.library.caltech.edu/records/a9d2k-ddj10/files/ja5044209_si_003.cif" }, { "basename": "ja5044209_si_004.pdf", "url": "https://authors.library.caltech.edu/records/a9d2k-ddj10/files/ja5044209_si_004.pdf" }, { "basename": "ja5044209.pdf", "url": "https://authors.library.caltech.edu/records/a9d2k-ddj10/files/ja5044209.pdf" }, { "basename": "ja5044209_si_001.cif", "url": "https://authors.library.caltech.edu/records/a9d2k-ddj10/files/ja5044209_si_001.cif" } ], "resource_type": "article", "pub_year": "2014", "author_list": "Lee, Sarah Yunmi; Neufeind, Stefan; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/9a5hn-pgh59", "eprint_id": 44725, "eprint_status": "archive", "datestamp": "2023-08-20 00:21:58", "lastmod": "2023-10-26 14:54:29", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Liang-Yufan", "name": { "family": "Liang", "given": "Yufan" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Catalytic Asymmetric Synthesis of Tertiary Alkyl Fluorides: Negishi Cross-Couplings of Racemic \u03b1,\u03b1-Dihaloketones", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. \n\nReceived: February 20, 2014; Published: March 31, 2014. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM62871). We thank Trixia M. Buscagan, Dr. Nathan D. Schley, Dr. Michael K. Takase (X-ray Crystallography Facility; a Bruker KAPPA APEX II X-ray diffractometer was purchased via NSF CRIF:MU award CHE-0639094 to the California Institute of Technology), and Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation) for assistance. \n\nThe authors declare no competing financial interest.\n\nPublished - ja501815p.pdf
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Supplemental Material - ja501815p_si_004.cif
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Supplemental Material - ja501815p_si_006.pdf
", "abstract": "The development of new approaches to the construction of fluorine-containing target molecules is important for a variety of scientific disciplines, including medicinal chemistry. In this Article, we describe a method for the catalytic enantioselective synthesis of tertiary alkyl fluorides through Negishi reactions of racemic \u03b1-halo-\u03b1-fluoroketones, which represents the first catalytic asymmetric cross-coupling that employs geminal dihalides as electrophiles. Thus, selective reaction of a C\u2013Br (or C\u2013Cl) bond in the presence of a C\u2013F bond can be achieved with the aid of a nickel/bis(oxazoline) catalyst. The products of the stereoconvergent cross-couplings, enantioenriched tertiary \u03b1-fluoroketones, can be converted into an array of interesting organofluorine compounds.", "date": "2014-04-09", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "136", "number": "14", "publisher": "American Chemical Society", "pagerange": "5520-5524", "id_number": "CaltechAUTHORS:20140408-083523386", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140408-083523386", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "NSF", "grant_number": "CHE-0639094" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1021/ja501815p", "pmcid": "PMC4004247", "primary_object": { "basename": "ja501815p.pdf", "url": "https://authors.library.caltech.edu/records/9a5hn-pgh59/files/ja501815p.pdf" }, "related_objects": [ { "basename": "ja501815p_si_001.cif", "url": "https://authors.library.caltech.edu/records/9a5hn-pgh59/files/ja501815p_si_001.cif" }, { "basename": "ja501815p_si_002.cif", "url": "https://authors.library.caltech.edu/records/9a5hn-pgh59/files/ja501815p_si_002.cif" }, { "basename": "ja501815p_si_003.cif", "url": "https://authors.library.caltech.edu/records/9a5hn-pgh59/files/ja501815p_si_003.cif" }, { "basename": "ja501815p_si_004.cif", "url": "https://authors.library.caltech.edu/records/9a5hn-pgh59/files/ja501815p_si_004.cif" }, { "basename": "ja501815p_si_005.cif", "url": "https://authors.library.caltech.edu/records/9a5hn-pgh59/files/ja501815p_si_005.cif" }, { "basename": "ja501815p_si_006.pdf", "url": "https://authors.library.caltech.edu/records/9a5hn-pgh59/files/ja501815p_si_006.pdf" } ], "resource_type": "article", "pub_year": "2014", "author_list": "Liang, Yufan and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/vgh4f-gx495", "eprint_id": 44118, "eprint_status": "archive", "datestamp": "2023-08-19 23:56:55", "lastmod": "2023-10-26 00:12:21", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Cong-Huan", "name": { "family": "Cong", "given": "Huan" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Catalytic Enantioselective Cyclization/Cross-Coupling with Alkyl Electrophiles", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. \n\nReceived: January 22, 2014. Publication Date (Web): February 27, 2014. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01-GM62871). We thank Yufan Liang, Dr. Allen G. Oliver (University of Notre Dame), Dr. Nathan D. Schley, and Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation) for assistance.\n\nPublished - ja500706v.pdf
Supplemental Material - ja500706v_si_001.cif
Supplemental Material - ja500706v_si_002.pdf
", "abstract": "As part of our ongoing effort to expand the scope of cross-coupling reactions of alkyl electrophiles, we have pursued a strategy wherein the nucleophilic coupling partner includes a pendant olefin; after transmetalation by such a substrate, if \u03b2-migratory insertion proceeds faster than direct cross-coupling, an additional carbon\u2013carbon bond and stereocenter can be formed. With the aid of a nickel/diamine catalyst (both components are commercially available), we have established the viability of this approach for the catalytic asymmetric synthesis of 2,3-dihydrobenzofurans and indanes. Furthermore, we have applied this new method to the construction of the dihydrobenzofuran core of fasiglifam, as well as to a cross-coupling with a racemic alkyl electrophile; in the latter process, the chiral catalyst controls two stereocenters, one that is newly generated in a \u03b2-migratory insertion and one that begins as a mixture of enantiomers.", "date": "2014-03-12", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "136", "number": "10", "publisher": "American Chemical Society", "pagerange": "3788-3791", "id_number": "CaltechAUTHORS:20140304-084532734", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140304-084532734", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1021/ja500706v", "pmcid": "PMC3985453", "primary_object": { "basename": "ja500706v.pdf", "url": "https://authors.library.caltech.edu/records/vgh4f-gx495/files/ja500706v.pdf" }, "related_objects": [ { "basename": "ja500706v_si_001.cif", "url": "https://authors.library.caltech.edu/records/vgh4f-gx495/files/ja500706v_si_001.cif" }, { "basename": "ja500706v_si_002.pdf", "url": "https://authors.library.caltech.edu/records/vgh4f-gx495/files/ja500706v_si_002.pdf" } ], "resource_type": "article", "pub_year": "2014", "author_list": "Cong, Huan and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/83n6x-5zn31", "eprint_id": 43521, "eprint_status": "archive", "datestamp": "2023-08-19 23:28:40", "lastmod": "2023-10-25 23:37:28", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Do-Hien-Quang", "name": { "family": "Do", "given": "Hien-Quang" } }, { "id": "Bachman-S", "name": { "family": "Bachman", "given": "Shoshana" } }, { "id": "Bissember-A-C", "name": { "family": "Bissember", "given": "Alex C." } }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Photoinduced, Copper-Catalyzed Alkylation of Amides with Unactivated Secondary Alkyl Halides at Room Temperature", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2014 American Chemical Society. \n\nReceived: December 12, 2013. Publication Date (Web): January 21, 2014. \n\nThis work was supported by the Gordon and Betty Moore Foundation. We acknowledge Prof. Rick L. Danheiser (MIT) for helpful discussions, and we thank Trixia M. Buscagan, Sidney E. Creutz, Gregory P. Harlow, Dr. Nathan D. Schley, Dr. David VanderVelde (Caltech NMR Facility), and Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation) for experimental assistance.\n\nSupplemental Material - ja4126609_si_001.cif
Supplemental Material - ja4126609_si_002.pdf
", "abstract": "The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for S_N2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate added ligand, and C\u2013N bond formation at room temperature. The method is compatible with a variety of functional groups, such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling pathway that includes photoexcitation of a copper\u2013amidate complex, followed by electron transfer to form an alkyl radical.", "date": "2014-02-05", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "136", "number": "5", "publisher": "American Chemical Society", "pagerange": "2162-2167", "id_number": "CaltechAUTHORS:20140127-095430890", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140127-095430890", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1021/ja4126609", "primary_object": { "basename": "ja4126609_si_001.cif", "url": "https://authors.library.caltech.edu/records/83n6x-5zn31/files/ja4126609_si_001.cif" }, "related_objects": [ { "basename": "ja4126609_si_002.pdf", "url": "https://authors.library.caltech.edu/records/83n6x-5zn31/files/ja4126609_si_002.pdf" } ], "resource_type": "article", "pub_year": "2014", "author_list": "Do, Hien-Quang; Bachman, Shoshana; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/r2qvv-y3p80", "eprint_id": 42845, "eprint_status": "archive", "datestamp": "2023-08-19 22:12:23", "lastmod": "2023-10-25 23:05:20", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Do-Hien-Quang", "name": { "family": "Do", "given": "Hien-Quang" } }, { "id": "Chandrashekar-E-R-R", "name": { "family": "Chandrashekar", "given": "E. R. R." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Nickel/Bis(oxazoline)-Catalyzed Asymmetric Negishi Arylations of Racemic Secondary Benzylic Electrophiles to Generate Enantioenriched 1,1-Diarylalkanes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 American Chemical Society. \n\nReceived: August 18, 2013; Published: October 28, 2013. \n\nSupport has been provided by the NIH (National Institute of General Medical Sciences: R01-GM62871) and Dr. Reddy's Laboratories (E.R.R.C.). We thank Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis, supported by the Gordon and Betty Moore Foundation) and Dr. Nathan D. Schley for assistance.\n\nAccepted Version - nihms535721.pdf
Supplemental Material - ja408561b_si_001.cif
Supplemental Material - ja408561b_si_002.pdf
", "abstract": "A tertiary stereogenic center that bears two different aryl substituents is found in a variety of bioactive compounds, including medicines such as Zoloft and Detrol. We have developed an efficient method for the synthesis of enantioenriched 1,1-diarylalkanes from readily available racemic benzylic alcohols. Formation of a benzylic mesylate (which is not isolated), followed by treatment with an arylzinc reagent, LiI, and a chiral nickel/bis(oxazoline) catalyst, furnishes the Negishi cross-coupling product in high ee and good yield. A wide array of functional groups (e.g., an aryl iodide, a thiophene, and an N-Boc-indole) are compatible with the mild reaction conditions. This method has been applied to a gram-scale synthesis of a precursor to Zoloft.", "date": "2013-11-06", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "135", "number": "44", "publisher": "American Chemical Society", "pagerange": "16288-16291", "id_number": "CaltechAUTHORS:20131205-082734303", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20131205-082734303", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Dr. Reddy's Laboratories" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1021/ja408561b", "pmcid": "PMC3869004", "primary_object": { "basename": "ja408561b_si_001.cif", "url": "https://authors.library.caltech.edu/records/r2qvv-y3p80/files/ja408561b_si_001.cif" }, "related_objects": [ { "basename": "ja408561b_si_002.pdf", "url": "https://authors.library.caltech.edu/records/r2qvv-y3p80/files/ja408561b_si_002.pdf" }, { "basename": "nihms535721.pdf", "url": "https://authors.library.caltech.edu/records/r2qvv-y3p80/files/nihms535721.pdf" } ], "resource_type": "article", "pub_year": "2013", "author_list": "Do, Hien-Quang; Chandrashekar, E. R. R.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/e1jhf-5eq14", "eprint_id": 43954, "eprint_status": "archive", "datestamp": "2023-08-19 21:24:01", "lastmod": "2023-10-26 00:02:27", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Ziegler-D-T", "name": { "family": "Ziegler", "given": "Daniel T." } }, { "id": "Choi-Junwon", "name": { "family": "Choi", "given": "Junwon" }, "orcid": "0000-0001-6004-5524" }, { "id": "Mu\u00f1oz-Molina-J-M", "name": { "family": "Mu\u00f1oz-Molina", "given": "Jos\u00e9 Mar\u00eda" } }, { "id": "Bissember-A-C", "name": { "family": "Bissember", "given": "Alex C." } }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "A Versatile Approach to Ullmann C\u2212N Couplings at Room Temperature: New Families of Nucleophiles and Electrophiles for Photoinduced, Copper-Catalyzed Processes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 American Chemical Society. \n\nPublished In Issue September 04, 2013; Article ASAP August 22, 2013; Received: June 17, 2013. \n\nJ.C. and J.M.M.-M. contributed equally to this work. \n\nThis work was supported by the Gordon and Betty Moore Foundation (grant to J.C.P.), the Kwanjeong Educational Foundation (fellowship to J.C.), and the Council for International Exchange of Scholars (Fulbright Scholar award to J.M.M.-M.). We thank the Caltech Center for Catalysis and Chemical Synthesis for use of instrumentation. D.T.Z. and J.C. are graduate students in the Department of Chemistry at the Massachusetts Institute of Technology. \n\nExperimental procedures and compound characterization data. This material is available free of charge via the Internet at http://pubs.acs.org.\n\nSupplemental Material - ja4060806_si_001.pdf
", "abstract": "The use of light to facilitate copper-catalyzed cross-couplings of nitrogen nucleophiles can enable C\u2212N bond formation to occur under unusually mild conditions. In this study, we substantially expand the scope of such processes, establishing that this approach is not limited to reactions of carbazoles with iodobenzene and alkyl halides. Specifically, we demonstrate for the first time that other nitrogen nucleophiles (e.g., common pharmacophores such as indoles, benzimidazoles, and imidazoles) as well\nas other electrophiles (e.g., hindered/deactivated/heterocyclic aryl iodides, an aryl bromide, an activated aryl chloride, alkenyl halides, and an alkynyl bromide) serve as suitable partners. Photoinduced C\u2212N bond formation can be achieved at room temperature using a common procedure with an inexpensive catalyst (CuI) that does\nnot require a ligand coadditive and is tolerant of moisture and a variety of functional groups.", "date": "2013-09-04", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "135", "number": "35", "publisher": "American Chemical Society", "pagerange": "13107-13112", "id_number": "CaltechAUTHORS:20140224-141339918", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140224-141339918", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "Kwanjeong Educational Foundation" }, { "agency": "Council for International Exchange of Scholars" } ] }, "doi": "10.1021/ja4060806", "primary_object": { "basename": "ja4060806_si_001.pdf", "url": "https://authors.library.caltech.edu/records/e1jhf-5eq14/files/ja4060806_si_001.pdf" }, "resource_type": "article", "pub_year": "2013", "author_list": "Ziegler, Daniel T.; Choi, Junwon; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/p908s-rkw96", "eprint_id": 42041, "eprint_status": "archive", "datestamp": "2023-08-19 20:52:52", "lastmod": "2023-10-25 15:03:17", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Cordier-C-J", "name": { "family": "Cordier", "given": "Christopher J." } }, { "id": "Lundgren-R-J", "name": { "family": "Lundgren", "given": "Ryan J." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Enantioconvergent Cross-Couplings of Racemic Alkylmetal Reagents with Unactivated Secondary Alkyl Electrophiles: Catalytic Asymmetric Negishi \u03b1-Alkylations of N-Boc-pyrrolidine", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 American Chemical Society. \n\nReceived: May 30, 2013; Published: July 19, 2013. \n\nWe thank the NIH NIGMS (R01-GM62871) for support and Dr. Scott C. Virgil (Caltech Center for Catalysis and Chemical Synthesis) and Dr. David G. VanderVelde (Caltech NMR facility) for assistance.\n\nAccepted Version - nihms508343.pdf
Supplemental Material - ja4054114_si_001.pdf
", "abstract": "Although enantioconvergent alkyl\u2013alkyl couplings of racemic electrophiles have been developed, there have been no reports of the corresponding reactions of racemic nucleophiles. Herein we describe Negishi cross-couplings of racemic \u03b1-zincated N-Boc-pyrrolidine with unactivated secondary halides, thus providing a one-pot, catalytic asymmetric method for the synthesis of a range of 2-alkylpyrrolidines (an important family of target molecules) from N-Boc-pyrrolidine, a commercially available precursor. Preliminary mechanistic studies indicated that two of the most straightforward mechanisms for enantioconvergence (dynamic kinetic resolution of the organometallic coupling partner and a simple \u03b2-hydride elimination/\u03b2-migratory insertion pathway) are unlikely to be operative.", "date": "2013-07-31", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "135", "number": "30", "publisher": "American Chemical Society", "pagerange": "10946-10949", "id_number": "CaltechAUTHORS:20131024-101621144", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20131024-101621144", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" } ] }, "doi": "10.1021/ja4054114", "pmcid": "PMC3803154", "primary_object": { "basename": "ja4054114_si_001.pdf", "url": "https://authors.library.caltech.edu/records/p908s-rkw96/files/ja4054114_si_001.pdf" }, "related_objects": [ { "basename": "nihms508343.pdf", "url": "https://authors.library.caltech.edu/records/p908s-rkw96/files/nihms508343.pdf" } ], "resource_type": "article", "pub_year": "2013", "author_list": "Cordier, Christopher J.; Lundgren, Ryan J.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/nk8n5-btb68", "eprint_id": 39911, "eprint_status": "archive", "datestamp": "2023-08-19 20:29:48", "lastmod": "2023-10-24 17:18:33", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Uyeda-Christopher", "name": { "family": "Uyeda", "given": "Christopher" }, "orcid": "0000-0001-9396-915X" }, { "id": "Tan-Yichen", "name": { "family": "Tan", "given": "Yichen" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "A New Family of Nucleophiles for Photoinduced, Copper-Catalyzed Cross-Couplings via Single-Electron Transfer: Reactions of Thiols with Aryl Halides Under Mild Conditions (0 \u00b0C)", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 American Chemical Society. \n\nReceived: April 23, 2013; Published: May 23, 2013. \n\nThis work was supported in part by the Gordon and Betty Moore Foundation. Insightful discussions with Kenneth J. Lotito as well as assistance with X-ray crystallography from Larry M. Henling are gratefully acknowledged.\n\nSupplemental Material - ja404050f_si_001.pdf
Supplemental Material - ja404050f_si_002.cif
", "abstract": "Building on the known photophysical properties of well-defined copper\u2013carbazolide complexes, we have recently described photoinduced, copper-catalyzed N-arylations and N-alkylations of carbazoles. Until now, there have been no examples of the use of other families of heteroatom nucleophiles in such photoinduced processes. Herein, we report a versatile photoinduced, copper-catalyzed method for coupling aryl thiols with aryl halides, wherein a single set of reaction conditions, using inexpensive CuI as a precatalyst without the need for an added ligand, is effective for a wide range of coupling partners. As far as we are aware, copper-catalyzed C\u2013S cross-couplings at 0 \u00b0C have not previously been achieved, which renders our observation of efficient reaction of an unactivated aryl iodide at \u221240 \u00b0C especially striking. Mechanistic investigations are consistent with these photoinduced C\u2013S cross-couplings following a SET/radical pathway for C\u2013X bond cleavage (via a Cu(I)\u2013thiolate), which contrasts with nonphotoinduced, copper-catalyzed processes wherein a concerted mechanism is believed to occur.", "date": "2013-06-26", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "135", "number": "25", "publisher": "American Chemical Society", "pagerange": "9548-9552", "id_number": "CaltechAUTHORS:20130814-104008585", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130814-104008585", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1021/ja404050f", "primary_object": { "basename": "ja404050f_si_001.pdf", "url": "https://authors.library.caltech.edu/records/nk8n5-btb68/files/ja404050f_si_001.pdf" }, "related_objects": [ { "basename": "ja404050f_si_002.cif", "url": "https://authors.library.caltech.edu/records/nk8n5-btb68/files/ja404050f_si_002.cif" } ], "resource_type": "article", "pub_year": "2013", "author_list": "Uyeda, Christopher; Tan, Yichen; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/rn7qv-k7b91", "eprint_id": 39006, "eprint_status": "archive", "datestamp": "2023-08-22 09:18:36", "lastmod": "2023-10-24 14:57:25", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Bissember-A-C", "name": { "family": "Bissember", "given": "Alex C." } }, { "id": "Lundgren-R-J", "name": { "family": "Lundgren", "given": "Rylan J." } }, { "id": "Creutz-S-E", "name": { "family": "Creutz", "given": "Sidney E." } }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Transition-Metal-Catalyzed Alkylations of Amines with Alkyl Halides: Photoinduced, Copper-Catalyzed Couplings of Carbazoles", "ispublished": "pub", "full_text_status": "public", "keywords": "alkylations; amine; copper; homogeneous catalysis; photochemistry", "note": "\u00a9 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. \n\nReceived: February 11, 2013; Published online: April 8, 2013. \n\nThis work was supported by the Gordon and Betty Moore Foundation (grant to J.C.P.), the National Science Foundation (fellowship support for S.E.C.), and the Natural Sciences and Engineering Research Council of Canada (fellowship support for R.J.L.). Assistance with X-ray crystallography from Larry M. Henling is gratefully acknowledged.\n\nSupplemental Material - anie_201301202_sm_miscellaneous_information.pdf
", "abstract": "N-alkylations of carbazoles with a variety of secondary and hindered primary alkyl iodides can be achieved by using a simple precatalyst (CuI) under mild conditions (0\u2009\u00b0C) in the presence of a Br\u00f8nsted base; at higher temperature (30\u2009\u00b0C), secondary alkyl bromides also serve as suitable coupling partners. A Li[Cu(carbazolide)_2] complex has been crystallographically characterized, and it may serve as an intermediate in the catalytic cycle.", "date": "2013-05-03", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "52", "number": "19", "publisher": "Wiley", "pagerange": "5129-5133", "id_number": "CaltechAUTHORS:20130620-145951306", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130620-145951306", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Gordon and Betty Moore Foundation" }, { "agency": "NSF" }, { "agency": "Natural Sciences and Engineering Research Council of Canada (NSERC)" } ] }, "doi": "10.1002/anie.201301202", "primary_object": { "basename": "anie_201301202_sm_miscellaneous_information.pdf", "url": "https://authors.library.caltech.edu/records/rn7qv-k7b91/files/anie_201301202_sm_miscellaneous_information.pdf" }, "resource_type": "article", "pub_year": "2013", "author_list": "Bissember, Alex C.; Lundgren, Rylan J.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/he0f7-nfy75", "eprint_id": 37620, "eprint_status": "archive", "datestamp": "2023-08-22 08:44:01", "lastmod": "2023-10-23 17:51:44", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lundgren-Rylan-J", "name": { "family": "Lundgren", "given": "Rylan J." } }, { "id": "Wilsily-Ashraf", "name": { "family": "Wilsily", "given": "Ashraf" } }, { "id": "Marion-Nicolas", "name": { "family": "Marion", "given": "Nicolas" } }, { "id": "Ma-Cong", "name": { "family": "Ma", "given": "Cong" } }, { "id": "Chung-Ying-Kit", "name": { "family": "Chung", "given": "Ying Kit" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Catalytic Asymmetric C-N Bond Formation: Phosphine-Catalyzed Intra- and Intermolecular \u03b3-Addition of Nitrogen Nucleophiles to Allenoates and Alkynoates", "ispublished": "pub", "full_text_status": "public", "keywords": "amination; asymmetric catalysis; heterocycles; organocatalysis; phosphanes", "note": "\u00a9 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. \n\nReceived: November 8, 2012; Published online: January 21, 2013. \n\nThis research has been supported by the National Institutes of\nHealth (National Institute of General Medical Sciences: R01-\nGM57034), the Natural Sciences and Engineering Research Council\nof Canada (postdoctoral fellowship for R.J.L.), the Laboratoire de\nSynth\u00e8se Organique, CNRS UMR 7652, Ecole Polytechnique DCSO,\nF91128 Palaiseau, France (fellowship for C.M.), and the Croucher\nFoundation (postdoctoral fellowship for Y.K.C.). We thank Shoshana\nBachman for a preliminary study.\n\nAccepted Version - nihms521614.pdf
Supplemental Material - anie_201208957_sm_miscellaneous_information.pdf
", "abstract": "Pin the amine on the gamma: A new method has been developed for the \u03b3-addition of nitrogen nucleophiles to \u03b3-substituted alkynoates or allenoates through intra- and intermolecular processes that are catalyzed by spirophosphine 1 (see scheme). An asymmetric version of this reaction affords enantioenriched pyrrolidines, indolines, and \u03b3-amino-\u03b1,\u03b2-unsaturated carbonyl compounds.", "date": "2013-02-25", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "52", "number": "9", "publisher": "Wiley", "pagerange": "2525-2528", "id_number": "CaltechAUTHORS:20130326-080903622", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130326-080903622", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM57034" }, { "agency": "Natural Sciences and Engineering Research Council of Canada (NSERC)" }, { "agency": "Laboratoire de Synth\u00e8se Organique" }, { "agency": "Centre National de la Recherche Scientifique (CNRS)", "grant_number": "UMR 7652" }, { "agency": "Ecole Polytechnique DCSO" }, { "agency": "Croucher Foundation" } ] }, "doi": "10.1002/anie.201208957", "pmcid": "PMC3819219", "primary_object": { "basename": "anie_201208957_sm_miscellaneous_information.pdf", "url": "https://authors.library.caltech.edu/records/he0f7-nfy75/files/anie_201208957_sm_miscellaneous_information.pdf" }, "related_objects": [ { "basename": "nihms521614.pdf", "url": "https://authors.library.caltech.edu/records/he0f7-nfy75/files/nihms521614.pdf" } ], "resource_type": "article", "pub_year": "2013", "author_list": "Lundgren, Rylan J.; Wilsily, Ashraf; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/0z1c9-z6j92", "eprint_id": 37050, "eprint_status": "archive", "datestamp": "2023-08-19 14:22:12", "lastmod": "2023-10-23 16:05:06", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Zultanski-S-L", "name": { "family": "Zultanski", "given": "Susan L." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Nickel-Catalyzed Carbon\u2212Carbon Bond-Forming Reactions of Unactivated Tertiary Alkyl Halides: Suzuki Arylations", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2013 American Chemical Society. \n\nReceived: November 29, 2012; published: January 2, 2013. \n\nSupport was provided by the National Institutes of Health (National Institute of General Medical Sciences, R01-GM62871) and Merck Research Laboratories (summer fellowship for S.L.Z.). We thank Dr. Alexander S. Dudnik for preliminary observations.\n\nPublished - ja311669p.pdf
Accepted Version - nihms-432697.pdf
Supplemental Material - ja311669p_si_001.pdf
", "abstract": "The first Suzuki cross-couplings of unactivated tertiary alkyl electrophiles are described. The method employs a readily accessible catalyst (NiBr_2\u00b7diglyme/4,4\u2032-di-tert-butyl-2,2\u2032-bipyridine, both commercially available) and represents the initial example of the use of a group 10 catalyst to cross-couple unactivated tertiary electrophiles to form C\u2013C bonds. This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group, in contrast with the umpolung strategy for this bond construction (cross-coupling of a tertiary alkylmetal with an aryl electrophile). Preliminary mechanistic studies are consistent with the generation of a radical intermediate along the reaction pathway.", "date": "2013-01-16", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "135", "number": "2", "publisher": "American Chemical Society", "pagerange": "624-627", "id_number": "CaltechAUTHORS:20130221-102120190", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20130221-102120190", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Merck Research Laboratories" } ] }, "doi": "10.1021/ja311669p", "pmcid": "PMC3547142", "primary_object": { "basename": "ja311669p_si_001.pdf", "url": "https://authors.library.caltech.edu/records/0z1c9-z6j92/files/ja311669p_si_001.pdf" }, "related_objects": [ { "basename": "nihms-432697.pdf", "url": "https://authors.library.caltech.edu/records/0z1c9-z6j92/files/nihms-432697.pdf" }, { "basename": "ja311669p.pdf", "url": "https://authors.library.caltech.edu/records/0z1c9-z6j92/files/ja311669p.pdf" } ], "resource_type": "article", "pub_year": "2013", "author_list": "Zultanski, Susan L. and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/0emam-qaa60", "eprint_id": 35683, "eprint_status": "archive", "datestamp": "2023-08-19 13:25:13", "lastmod": "2023-10-20 20:28:59", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Creutz-S-E", "name": { "family": "Creutz", "given": "Sidney E." } }, { "id": "Lotito-K-J", "name": { "family": "Lotito", "given": "Kenneth J." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" }, { "id": "Peters-J-C", "name": { "family": "Peters", "given": "Jonas C." }, "orcid": "0000-0002-6610-4414" } ] }, "title": "Photoinduced Ullmann C\u2013N Coupling: Demonstrating the Viability of a Radical Pathway", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Association for the Advancement of Science. \n\nReceived 22 June 2012; accepted 10 September 2012. \n\nThis work was supported by the National Science Foundation (graduate research fellowships for S.E.C. and K.J.L.) and by the Gordon and Betty Moore Foundation. Metrical parameters for the structure of copper complex 1 are available free of charge from the Cambridge Crystallographic Data Centre under reference CCDC-896019.\n\nSupplemental Material - Creutz-SOM.pdf
", "abstract": "Carbon\u2013nitrogen (C\u2013N) bond-forming reactions of amines with aryl halides to generate arylamines (anilines), mediated by a stoichiometric copper reagent at elevated temperature (>180\u00b0C), were first described by Ullmann in 1903. In the intervening century, this and related C\u2013N bond-forming processes have emerged as powerful tools for organic synthesis. Here, we report that Ullmann C\u2013N coupling can be photoinduced by using a stoichiometric or a catalytic amount of copper, which enables the reaction to proceed under unusually mild conditions (room temperature or even \u201340\u00b0C). An array of data are consistent with a single-electron transfer mechanism, representing the most substantial experimental support to date for the viability of this pathway for Ullmann C\u2013N couplings.", "date": "2012-11-02", "date_type": "published", "publication": "Science", "volume": "338", "number": "6107", "publisher": "American Association for the Advancement of Science", "pagerange": "647-651", "id_number": "CaltechAUTHORS:20121127-143024844", "issn": "0036-8075", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20121127-143024844", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF Graduate Research Fellowship" }, { "agency": "Gordon and Betty Moore Foundation" } ] }, "doi": "10.1126/science.1226458", "primary_object": { "basename": "Creutz-SOM.pdf", "url": "https://authors.library.caltech.edu/records/0emam-qaa60/files/Creutz-SOM.pdf" }, "resource_type": "article", "pub_year": "2012", "author_list": "Creutz, Sidney E.; Lotito, Kenneth J.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/znt1k-c4885", "eprint_id": 35813, "eprint_status": "archive", "datestamp": "2023-08-19 13:11:59", "lastmod": "2023-10-20 21:11:28", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Binder-J-T", "name": { "family": "Binder", "given": "J\u00f6rg T." } }, { "id": "Cordier-C-J", "name": { "family": "Cordier", "given": "Christopher J." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Catalytic Enantioselective Cross-Couplings of Secondary Alkyl Electrophiles with Secondary Alkylmetal Nucleophiles: Negishi Reactions of Racemic Benzylic Bromides with Achiral Alkylzinc Reagents", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society. \n\nReceived: August 25, 2012. Publication Date (Web): October 5, 2012. \n\nSupport has been provided by the National Institutes of Health\n(National Institute of General Medical Sciences: R01-GM62871) and the German Academic Exchange Service (postdoctoral fellowship for J.T.B.). \n\n The authors declare no competing financial interest.\n\nPublished - ja308460z.pdf
Accepted Version - nihms-413387.pdf
Supplemental Material - ja308460z_si_001.pdf
", "abstract": "We have developed a nickel-catalyzed method for the asymmetric cross-coupling of secondary electrophiles with secondary nucleophiles, specifically, stereoconvergent Negishi reactions of racemic benzylic bromides with achiral cycloalkylzinc reagents. In contrast to most previous studies of enantioselective Negishi cross-couplings, tridentate pybox ligands are ineffective in this process; however, a new, readily available bidentate isoquinoline\u2013oxazoline ligand furnishes excellent ee's and good yields. The use of acyclic alkylzinc reagents as coupling partners led to the discovery of a highly unusual isomerization that generates a significant quantity of a branched cross-coupling product from an unbranched nucleophile.", "date": "2012-10-17", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "41", "publisher": "American Chemical Society", "pagerange": "17003-17006", "id_number": "CaltechAUTHORS:20121205-093544858", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20121205-093544858", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Deutscher Akademischer Austauschdienst (DAAD)" } ] }, "doi": "10.1021/ja308460z", "pmcid": "PMC3474870", "primary_object": { "basename": "ja308460z.pdf", "url": "https://authors.library.caltech.edu/records/znt1k-c4885/files/ja308460z.pdf" }, "related_objects": [ { "basename": "ja308460z_si_001.pdf", "url": "https://authors.library.caltech.edu/records/znt1k-c4885/files/ja308460z_si_001.pdf" }, { "basename": "nihms-413387.pdf", "url": "https://authors.library.caltech.edu/records/znt1k-c4885/files/nihms-413387.pdf" } ], "resource_type": "article", "pub_year": "2012", "author_list": "Binder, J\u00f6rg T.; Cordier, Christopher J.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/a7cg5-xp060", "eprint_id": 35217, "eprint_status": "archive", "datestamp": "2023-08-19 12:41:40", "lastmod": "2023-10-20 15:51:39", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lee-Sarah-Yunmi", "name": { "family": "Lee", "given": "Sarah Yunmi" } }, { "id": "Murphy-J-M", "name": { "family": "Murphy", "given": "Jaclyn M." } }, { "id": "Ukai-Atsushi", "name": { "family": "Ukai", "given": "Atsushi" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Nonenzymatic Dynamic Kinetic Resolution of Secondary Alcohols via Enantioselective Acylation: Synthetic and Mechanistic Studies", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society. \n\nReceived: July 27, 2012. Published: August 30, 2012. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences: R01\u2212GM057034 for G.C.F. and F32 GM087889 for J.M.M.) and by the Global COE in Chemistry, Nagoya University (fellowship to A.U.). We thank Dr. Jeffrey H. Simpson (Department of Chemistry Instrumentation Facility) for assistance with NMR spectroscopy, Dr. Peter M\u00fcller for assistance with X-ray crystallography (and NSF grant CHE-0946721 for the purchase of an X-ray diffractomer), and Dr. Gerald B. Rowland for preliminary studies.\n\nPublished - ja307425g.pdf
Accepted Version - nihms-404669.pdf
Supplemental Material - ja307425g_si_001.pdf
Supplemental Material - ja307425g_si_002.cif
", "abstract": "Because of the ubiquity of the secondary carbinol subunit, the development of new methods for its enantioselective synthesis remains an important ongoing challenge. In this report, we describe the first nonenzymatic method for the dynamic kinetic resolution (DKR) of secondary alcohols (specifically, aryl alkyl carbinols) through enantioselective acylation, and we substantially expand the scope of this approach, vis-\u00e0-vis enzymatic reactions. Simply combining an effective process for the kinetic resolution of alcohols with an active catalyst for the racemization of alcohols did not lead to DKR, due to the incompatibility of the ruthenium-based racemization catalyst with the acylating agent (Ac_2O) used in the kinetic resolution. A mechanistic investigation revealed that the ruthenium catalyst is deactivated through the formation of a stable ruthenium\u2013acetate complex; this deleterious pathway was circumvented through the appropriate choice of acylating agent (an acyl carbonate). Mechanistic studies of this new process point to reversible N-acylation of the nucleophilic catalyst, acyl transfer from the catalyst to the alcohol as the rate-determining step, and carbonate anion serving as the Br\u00f8nsted base in that acyl-transfer step.", "date": "2012-09-12", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "36", "publisher": "American Chemical Society", "pagerange": "15149-15153", "id_number": "CaltechAUTHORS:20121031-144133793", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20121031-144133793", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM057034" }, { "agency": "NIH Postdoctoral Fewllowship", "grant_number": "F32 GM087889" }, { "agency": "Nagoya University" }, { "agency": "NSF", "grant_number": "CHE-0946721" } ] }, "doi": "10.1021/ja307425g", "pmcid": "PMC3447740", "primary_object": { "basename": "ja307425g.pdf", "url": "https://authors.library.caltech.edu/records/a7cg5-xp060/files/ja307425g.pdf" }, "related_objects": [ { "basename": "ja307425g_si_001.pdf", "url": "https://authors.library.caltech.edu/records/a7cg5-xp060/files/ja307425g_si_001.pdf" }, { "basename": "ja307425g_si_002.cif", "url": "https://authors.library.caltech.edu/records/a7cg5-xp060/files/ja307425g_si_002.cif" }, { "basename": "nihms-404669.pdf", "url": "https://authors.library.caltech.edu/records/a7cg5-xp060/files/nihms-404669.pdf" } ], "resource_type": "article", "pub_year": "2012", "author_list": "Lee, Sarah Yunmi; Murphy, Jaclyn M.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/5wahh-ndx22", "eprint_id": 35219, "eprint_status": "archive", "datestamp": "2023-08-19 12:25:20", "lastmod": "2023-10-20 15:51:43", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Bissember-A-C", "name": { "family": "Bissember", "given": "Alex C." } }, { "id": "Levina-A", "name": { "family": "Levina", "given": "Anna" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "A Mild, Palladium-Catalyzed Method for the Dehydrohalogenation of Alkyl Bromides: Synthetic and Mechanistic Studies", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society. \n\nReceived: June 28, 2012. Published: August 20, 2012. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM62871), an American Australian Association Merck Company Foundation Fellowship (A.C.B.), the Paul E. Gray (1954) Endowed Fund for the Undergraduate Research Opportunities Program (A.L.), and the John Reed Fund (A.L.).\n\nPublished - ja306323x.pdf
Accepted Version - nihms-402431.pdf
Supplemental Material - ja306323x_si_001.pdf
", "abstract": "We have exploited a typically undesired elementary step in cross-coupling reactions, \u03b2-hydride elimination, to accomplish palladium-catalyzed dehydrohalogenations of alkyl bromides to form terminal olefins. We have applied this method, which proceeds in excellent yield at room temperature in the presence of a variety of functional groups, to a formal total synthesis of (R)-mevalonolactone. Our mechanistic studies have established that the rate-determining step can vary with the structure of the alkyl bromide and, most significantly, that L_2PdHBr (L = phosphine), an intermediate that is often invoked in palladium-catalyzed processes such as the Heck reaction, is not an intermediate in the active catalytic cycle.", "date": "2012-08-29", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "34", "publisher": "American Chemical Society", "pagerange": "14232-14237", "id_number": "CaltechAUTHORS:20121031-150625941", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20121031-150625941", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "American Australian Association Merck Company Foundation Fellowship" }, { "agency": "Paul E. Gray Endowed Fund for Undergraduate Research Opportunities Program" }, { "agency": "John Reed Fund" } ] }, "doi": "10.1021/ja306323x", "pmcid": "PMC3432975", "primary_object": { "basename": "ja306323x.pdf", "url": "https://authors.library.caltech.edu/records/5wahh-ndx22/files/ja306323x.pdf" }, "related_objects": [ { "basename": "ja306323x_si_001.pdf", "url": "https://authors.library.caltech.edu/records/5wahh-ndx22/files/ja306323x_si_001.pdf" }, { "basename": "nihms-402431.pdf", "url": "https://authors.library.caltech.edu/records/5wahh-ndx22/files/nihms-402431.pdf" } ], "resource_type": "article", "pub_year": "2012", "author_list": "Bissember, Alex C.; Levina, Anna; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/1vqr3-v2k75", "eprint_id": 102846, "eprint_status": "archive", "datestamp": "2023-08-19 11:29:01", "lastmod": "2023-10-20 00:33:03", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Dudnik-A-S", "name": { "family": "Dudnik", "given": "Alexander S." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Nickel-Catalyzed Coupling Reactions of Alkyl Electrophiles, Including Unactivated Tertiary Halides, To Generate Carbon\u2013Boron Bonds", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society. \n\nReceived: April 27, 2012. Published: June 6, 2012. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, grant R01-GM62871). We thank Dr. Ashraf Wilsily for experimental assistance. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms383249.pdf
Supplemental Material - ja304068t_si_001.pdf
", "abstract": "Through the use of a catalyst formed in situ from NiBr2\u00b7diglyme and a pybox ligand (both of which are commercially available), we have achieved our first examples of coupling reactions of unactivated tertiary alkyl electrophiles, as well as our first success with nickel-catalyzed couplings that generate bonds other than C\u2013C bonds. Specifically, we have determined that this catalyst accomplishes Miyaura-type borylations of unactivated tertiary, secondary, and primary alkyl halides with diboron reagents to furnish alkylboronates, a family of compounds with substantial (and expanding) utility, under mild conditions; indeed, the umpolung borylation of a tertiary alkyl bromide can be achieved at a temperature as low as \u221210 \u00b0C. The method exhibits good functional-group compatibility and is regiospecific, both of which can be issues with traditional approaches to the synthesis of alkylboronates. In contrast to seemingly related nickel-catalyzed C\u2013C bond-forming processes, tertiary halides are more reactive than secondary or primary halides in this nickel-catalyzed C\u2013B bond-forming reaction; this divergence is particularly noteworthy in view of the likelihood that both transformations follow an inner-sphere electron-transfer pathway for oxidative addition.", "date": "2012-06-27", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "25", "publisher": "American Chemical Society", "pagerange": "10693-10697", "id_number": "CaltechAUTHORS:20200428-095144864", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095144864", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" } ] }, "doi": "10.1021/ja304068t", "pmcid": "PMC3384763", "primary_object": { "basename": "ja304068t_si_001.pdf", "url": "https://authors.library.caltech.edu/records/1vqr3-v2k75/files/ja304068t_si_001.pdf" }, "related_objects": [ { "basename": "nihms383249.pdf", "url": "https://authors.library.caltech.edu/records/1vqr3-v2k75/files/nihms383249.pdf" } ], "resource_type": "article", "pub_year": "2012", "author_list": "Dudnik, Alexander S. and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/ywjk3-z4t35", "eprint_id": 48840, "eprint_status": "archive", "datestamp": "2023-08-19 11:19:21", "lastmod": "2023-10-17 20:28:31", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Choi-Junwon", "name": { "family": "Choi", "given": "Junwon" }, "orcid": "0000-0001-6004-5524" }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Catalytic asymmetric synthesis of secondary nitriles via stereoconvergent Negishi arylations and alkenylations of racemic \u03b1-bromonitriles", "ispublished": "pub", "full_text_status": "public", "note": "Copyright \u00a9 2012 American Chemical Society. \n\nReceived: April 10, 2012. Article ASAP May 21, 2012. Published In Issue June 06, 2012. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, grant R01-GM62871) and the Kwanjeong Educational Foundation (fellowship to J.C.). We thank Dr. Ashraf Wilsily for assistance in the preparation of substrates. \n\nThe authors declare no competing financial interest. \n\nSupporting Information: Experimental procedures and compound characterization data. This material is available free of charge via the Internet at http://pubs.acs.org.\n\nAccepted Version - nihms379312.pdf
Supplemental Material - ja303442q_si_001.cif
Supplemental Material - ja303442q_si_002.cif
Supplemental Material - ja303442q_si_003.pdf
", "abstract": "The first method for the stereoconvergent cross-coupling of racemic \u03b1-halonitriles is described, specifically, nickel-catalyzed Negishi arylations and alkenylations that furnish an array of enantioenriched \u03b1-arylnitriles and allylic nitriles, respectively. Noteworthy features of this investigation include: the highly enantioselective synthesis of \u03b1-alkyl-\u03b1-aryl nitriles that bear secondary \u03b1-alkyl substituents; the first examples of the use of alkenylzinc reagents in stereoconvergent Negishi reactions of alkyl electrophiles; demonstration of the utility of a new family of ligands for asymmetric Negishi cross-couplings (a bidentate bis(oxazoline), rather than a tridentate pybox); in the case of arylzinc reagents, carbon\u2013carbon bond formation at a remarkably low temperature (\u221278 \u00b0C), the lowest reported to date for an enantioselective cross-coupling of an alkyl electrophile; a mechanistic dichotomy between Negishi reactions of an unactivated versus an activated secondary alkyl bromide.", "date": "2012-06-06", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "22", "publisher": "American Chemical Society", "pagerange": "9102-9105", "id_number": "CaltechAUTHORS:20140825-100734890", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140825-100734890", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Kwanjeong Educational Foundation" } ] }, "doi": "10.1021/ja303442q", "pmcid": "PMC3415582", "primary_object": { "basename": "ja303442q_si_001.cif", "url": "https://authors.library.caltech.edu/records/ywjk3-z4t35/files/ja303442q_si_001.cif" }, "related_objects": [ { "basename": "ja303442q_si_002.cif", "url": "https://authors.library.caltech.edu/records/ywjk3-z4t35/files/ja303442q_si_002.cif" }, { "basename": "ja303442q_si_003.pdf", "url": "https://authors.library.caltech.edu/records/ywjk3-z4t35/files/ja303442q_si_003.pdf" }, { "basename": "nihms379312.pdf", "url": "https://authors.library.caltech.edu/records/ywjk3-z4t35/files/nihms379312.pdf" } ], "resource_type": "article", "pub_year": "2012", "author_list": "Choi, Junwon and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/vjjhv-5hw75", "eprint_id": 102848, "eprint_status": "archive", "datestamp": "2023-08-22 05:25:44", "lastmod": "2023-10-20 00:33:08", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Wilsily-A", "name": { "family": "Wilsily", "given": "Ashraf" } }, { "id": "Tramutola-F", "name": { "family": "Tramutola", "given": "Francesco" } }, { "id": "Owston-N-A", "name": { "family": "Owston", "given": "Nathan A." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "New Directing Groups for Metal-Catalyzed Asymmetric Carbon\u2013Carbon Bond-Forming Processes: Stereoconvergent Alkyl\u2013Alkyl Suzuki Cross-Couplings of Unactivated Electrophiles", "ispublished": "pub", "full_text_status": "public", "keywords": "Amines; Electrophiles; Sulfones; Alkyls; Cross coupling reaction", "note": "\u00a9 2012 American Chemical Society. \n\nReceived: February 17, 2012. Published: March 26, 2012. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, grant R01-GM62871) and the University of Basilicata (fellowship to F.T.). We thank Dr. Jeffrey H. Simpson (Department of Chemistry Instrumentation Facility) for assistance with NMR spectroscopy. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms366375.pdf
Supplemental Material - ja301612y_si_001.pdf
", "abstract": "The ability of two common protected forms of amines (carbamates and sulfonamides) to serve as directing groups in Ni-catalyzed Suzuki reactions has been exploited in the development of catalytic asymmetric methods for cross-coupling unactivated alkyl electrophiles. Racemic secondary bromides and chlorides undergo C\u2013C bond formation in a stereoconvergent process in good ee at room temperature in the presence of a commercially available Ni complex and chiral ligand. Structure\u2013enantioselectivity studies designed to elucidate the site of binding to Ni (the oxygen of the carbamate and of the sulfonamide) led to the discovery that sulfones also serve as useful directing groups for asymmetric Suzuki cross-couplings of racemic alkyl halides. To our knowledge, this investigation provides the first examples of the use of sulfonamides or sulfones as effective directing groups in metal-catalyzed asymmetric C\u2013C bond-forming reactions. A mechanistic study established that transmetalation occurs with retention of stereochemistry and that the resulting Ni\u2013C bond does not undergo homolysis in subsequent stages of the catalytic cycle.", "date": "2012-04-04", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "13", "publisher": "American Chemical Society", "pagerange": "5794-5797", "id_number": "CaltechAUTHORS:20200428-095145201", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095145201", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "University of Basilicata" } ] }, "doi": "10.1021/ja301612y", "pmcid": "PMC3333791", "primary_object": { "basename": "ja301612y_si_001.pdf", "url": "https://authors.library.caltech.edu/records/vjjhv-5hw75/files/ja301612y_si_001.pdf" }, "related_objects": [ { "basename": "nihms366375.pdf", "url": "https://authors.library.caltech.edu/records/vjjhv-5hw75/files/nihms366375.pdf" } ], "resource_type": "article", "pub_year": "2012", "author_list": "Wilsily, Ashraf; Tramutola, Francesco; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/nv0bn-xd674", "eprint_id": 102850, "eprint_status": "archive", "datestamp": "2023-08-19 10:21:05", "lastmod": "2023-10-20 00:33:13", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Zuhl-A-M", "name": { "family": "Zuhl", "given": "Andrea M." } }, { "id": "Mohr-J-T", "name": { "family": "Mohr", "given": "Justin T." }, "orcid": "0000-0002-7005-3322" }, { "id": "Bachovchin-D-A", "name": { "family": "Bachovchin", "given": "Daniel A." } }, { "id": "Niessen-Sherry", "name": { "family": "Niessen", "given": "Sherry" } }, { "id": "Hsu-Ku-Lung", "name": { "family": "Hsu", "given": "Ku-Lung" } }, { "id": "Berlin-J-M", "name": { "family": "Berlin", "given": "Jacob M." }, "orcid": "0000-0001-7498-766X" }, { "id": "Dochnahl-Maximilian", "name": { "family": "Dochnahl", "given": "Maximilian" } }, { "id": "L\u00f3pez-Alberca-M-P", "name": { "family": "L\u00f3pez-Alberca", "given": "Mar\u00eda P." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" }, { "id": "Cravatt-B-F", "name": { "family": "Cravatt", "given": "Benjamin F." } } ] }, "title": "Competitive Activity-Based Protein Profiling Identifies Aza-\u03b2-Lactams as a Versatile Chemotype for Serine Hydrolase Inhibition", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society, \n\nReceived: January 24, 2012. Published: March 8, 2012. \n\nWe thank B. Kipper, K. Masuda, D. Milliken, J. Murphy, H. Pugh, and K. Tsuboi for technical assistance. This work was supported by National Institutes of Health grants CA132630 and GM090294 (B.F.C.), GM57034 (G.C.F.), and GM086040 (postdoctoral fellowship to J.T.M.); the National Science Foundation (predoctoral fellowships to A.M.Z.. and D.A.B.); the California Breast Cancer Research Program (predoctoral fellowship to D.A.B.); Hewitt Foundation for Medical Research (postdoctoral fellowship to K.L.H.); the German Academic Exchange Service (postdoctoral fellowship to M.D.); Spanish Ministry of Education (FECYT, postdoctoral fellowship to M.P.L.A.); Abide Therapeutics; and The Skaggs Institute for Chemical Biology. \n\nThe authors declare the following competing financial interest(s): Drs. Cravatt and Fu are advisors for a company interested in developing serine hydrolase inhibitors as new therapeutics.\n\nAccepted Version - nihms362738.pdf
Supplemental Material - ja300799t_si_001.pdf
", "abstract": "Serine hydrolases are one of the largest and most diverse enzyme classes in Nature. Most serine hydrolases lack selective inhibitors, which are valuable probes for assigning functions to these enzymes. We recently discovered a set of aza-\u03b2-lactams (ABLs) that act as potent and selective inhibitors of the mammalian serine hydrolase protein-phosphatase methylesterase-1 (PME-1). The ABLs inactivate PME-1 by covalent acylation of the enzyme's serine nucleophile, suggesting that they could offer a general scaffold for serine hydrolase inhibitor discovery. Here, we have tested this hypothesis by screening ABLs more broadly against cell and tissue proteomes by competitive activity-based protein profiling (ABPP), leading to the discovery of lead inhibitors for several serine hydrolases, including the uncharacterized enzyme \u03b1,\u03b2-hydrolase domain-containing 10 (ABHD10). ABPP-guided medicinal chemistry yielded a compound ABL303 that potently (IC\u2085\u2080 \u2248 30 nM) and selectively inactivated ABHD10 in vitro and in living cells. A comparison of optimized inhibitors for PME-1 and ABHD10 indicates that modest structural changes that alter steric bulk can tailor the ABL to selectively react with distinct, distantly related serine hydrolases. Our findings, taken together, designate the ABL as a versatile reactive group for creating first-in-class serine hydrolase inhibitors.", "date": "2012-03-21", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "11", "publisher": "American Chemical Society", "pagerange": "5068-5071", "id_number": "CaltechAUTHORS:20200428-095145436", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095145436", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "CA132630" }, { "agency": "NIH", "grant_number": "GM090294" }, { "agency": "NIH", "grant_number": "GM57034" }, { "agency": "NIH Postdoctoral Fellowship", "grant_number": "GM086040" }, { "agency": "NSF Graduate Research Fellowship" }, { "agency": "California Breast Cancer Research Program" }, { "agency": "Hewitt Foundation for Medical Research" }, { "agency": "Deutscher Akademischer Austauschdienst (DAAD)" }, { "agency": "Fundaci\u00f3n Espa\u00f1ola para la Ciencia y la Tecnolog\u00eda (FECYT)" }, { "agency": "Abide Therapeutics" }, { "agency": "Skaggs Institute for Chemical Biology" } ] }, "doi": "10.1021/ja300799t", "pmcid": "PMC3326416", "primary_object": { "basename": "ja300799t_si_001.pdf", "url": "https://authors.library.caltech.edu/records/nv0bn-xd674/files/ja300799t_si_001.pdf" }, "related_objects": [ { "basename": "nihms362738.pdf", "url": "https://authors.library.caltech.edu/records/nv0bn-xd674/files/nihms362738.pdf" } ], "resource_type": "article", "pub_year": "2012", "author_list": "Zuhl, Andrea M.; Mohr, Justin T.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/7cjv3-9et22", "eprint_id": 102851, "eprint_status": "archive", "datestamp": "2023-08-19 09:58:13", "lastmod": "2023-10-20 00:33:18", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Oelke-A-J", "name": { "family": "Oelke", "given": "Alexander J." } }, { "id": "Sun-Jianwei", "name": { "family": "Sun", "given": "Jianwei" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Nickel-Catalyzed Enantioselective Cross-Couplings of Racemic Secondary Electrophiles That Bear an Oxygen Leaving Group", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2012 American Chemical Society. \n\nReceived: January 2, 2012. Published: February 1, 2012. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, grant R01-GM62871) and the Alexander von Humboldt Foundation (research fellowship for A.J.O.). We thank Dr. Wataru Muramatsu for a preliminary investigation. \n\nThe authors declare no competing financial interest.\n\nAccepted Version - nihms-354532.pdf
Supplemental Material - ja300031w_si_001.pdf
", "abstract": "To date, effective nickel-catalyzed enantioselective cross-couplings of alkyl electrophiles that bear oxygen leaving groups have been limited to reactions of allylic alcohol derivatives with Grignard reagents. In this Communication, we establish that, in the presence of a nickel/pybox catalyst, a variety of racemic propargylic carbonates are suitable partners for asymmetric couplings with organozinc reagents. The method is compatible with an array of functional groups and utilizes commercially available catalyst components. The development of a versatile nickel-catalyzed enantioselective cross-coupling process for electrophiles that bear a leaving group other than a halide adds a significant new dimension to the scope of these reactions.", "date": "2012-02-15", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "134", "number": "6", "publisher": "American Chemical Society", "pagerange": "2966-2969", "id_number": "CaltechAUTHORS:20200428-095145561", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095145561", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Alexander von Humboldt Foundation" } ] }, "doi": "10.1021/ja300031w", "pmcid": "PMC3288265", "primary_object": { "basename": "ja300031w_si_001.pdf", "url": "https://authors.library.caltech.edu/records/7cjv3-9et22/files/ja300031w_si_001.pdf" }, "related_objects": [ { "basename": "nihms-354532.pdf", "url": "https://authors.library.caltech.edu/records/7cjv3-9et22/files/nihms-354532.pdf" } ], "resource_type": "article", "pub_year": "2012", "author_list": "Oelke, Alexander J.; Sun, Jianwei; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/cp6pq-60v85", "eprint_id": 103148, "eprint_status": "archive", "datestamp": "2023-08-19 08:35:30", "lastmod": "2023-10-20 15:42:10", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Fujiwara-Yuji", "name": { "family": "Fujiwara", "given": "Yuji" } }, { "id": "Sun-Jianwei", "name": { "family": "Sun", "given": "Jianwei" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Enantioselective carbon\u2013sulfur bond formation: \u03b3 additions of aryl thiols to allenoates catalyzed by a chiral phosphepine", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2011 The Royal Society of Chemistry. \n\nReceived 29th June 2011, Accepted 1st August 2011, First published on 25th August 2011. \n\nSupport was provided by the National Institute of Health (National Institute of General Medical Sciences, grant R01-GM57034) and Dainippon Sumitomo Pharma Co., Ltd. (fellowship for Y.F.). We thank Dr Jonathan E. Wilson for a preliminary study.\n\nPublished - c1sc00414j.pdf
Accepted Version - nihms343995.pdf
Supplemental Material - c1sc00414j.txt
Supplemental Material - c1sc00414j_si.pdf
", "abstract": "An effective phosphine-catalyzed method was developed for the enantioselective addition of aryl thiols to the \u03b3 position of allenoates, thereby providing ready access to aryl alkyl sulfides in very good ee. The array of mechanistic data are consistent with the addition of the chiral phosphine to the allenoate being the turnover-limiting step of the catalytic cycle. The optimized reaction conditions, as well as the mechanistic observations, differ markedly from an earlier report on asymmetric additions of alkylthiols to allenoates, which highlights the potential for divergent behavior between alkyl and aryl thiols when acting as nucleophiles.", "date": "2011-11-01", "date_type": "published", "publication": "Chemical Science", "volume": "2", "number": "11", "publisher": "Royal Society of Chemistry", "pagerange": "2196-2198", "id_number": "CaltechAUTHORS:20200512-133335212", "issn": "2041-6520", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200512-133335212", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM57034" }, { "agency": "Dainippon Sumitomo Pharma Co., Ltd." } ] }, "doi": "10.1039/c1sc00414j", "pmcid": "PMC3248350", "primary_object": { "basename": "c1sc00414j.pdf", "url": "https://authors.library.caltech.edu/records/cp6pq-60v85/files/c1sc00414j.pdf" }, "related_objects": [ { "basename": "c1sc00414j.txt", "url": "https://authors.library.caltech.edu/records/cp6pq-60v85/files/c1sc00414j.txt" }, { "basename": "c1sc00414j_si.pdf", "url": "https://authors.library.caltech.edu/records/cp6pq-60v85/files/c1sc00414j_si.pdf" }, { "basename": "nihms343995.pdf", "url": "https://authors.library.caltech.edu/records/cp6pq-60v85/files/nihms343995.pdf" } ], "resource_type": "article", "pub_year": "2011", "author_list": "Fujiwara, Yuji; Sun, Jianwei; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/m5yd0-xrf49", "eprint_id": 102852, "eprint_status": "archive", "datestamp": "2023-08-19 08:19:14", "lastmod": "2023-10-20 00:33:23", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Zultanski-S-L", "name": { "family": "Zultanski", "given": "Susan L." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Catalytic Asymmetric \u03b3-Alkylation of Carbonyl Compounds via Stereoconvergent Suzuki Cross-Couplings", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2011 American Chemical Society. \n\nReceived: August 22, 2011. Published: September 13, 2011. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM62871), a Merck Summer Fellowship (S.L.Z.), and a Robert T. Haslam Graduate Fellowship (S.L.Z.).\n\nAccepted Version - nihms324923.pdf
Supplemental Material - ja2079515_si_001.cif
Supplemental Material - ja2079515_si_002.pdf
", "abstract": "With the aid of a chiral nickel catalyst, enantioselective \u03b3- (and \u03b4-) alkylations of carbonyl compounds can be achieved through the coupling of \u03b3-haloamides with alkylboranes. In addition to primary alkyl nucleophiles, for the first time for an asymmetric cross-coupling of an unactivated alkyl electrophile, an arylmetal, a boronate ester, and a secondary (cyclopropyl) alkylmetal compound are shown to couple with significant enantioselectivity. A mechanistic study indicates that cleavage of the carbon\u2013halogen bond of the electrophile is irreversible under the conditions for asymmetric carbon\u2013carbon bond formation.", "date": "2011-10-05", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "133", "number": "39", "publisher": "American Chemical Society", "pagerange": "15362-15364", "id_number": "CaltechAUTHORS:20200428-095145670", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095145670", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Merck" }, { "agency": "Massachusetts Institute of Technology (MIT)" } ] }, "doi": "10.1021/ja2079515", "pmcid": "PMC3183125", "primary_object": { "basename": "ja2079515_si_001.cif", "url": "https://authors.library.caltech.edu/records/m5yd0-xrf49/files/ja2079515_si_001.cif" }, "related_objects": [ { "basename": "ja2079515_si_002.pdf", "url": "https://authors.library.caltech.edu/records/m5yd0-xrf49/files/ja2079515_si_002.pdf" }, { "basename": "nihms324923.pdf", "url": "https://authors.library.caltech.edu/records/m5yd0-xrf49/files/nihms324923.pdf" } ], "resource_type": "article", "pub_year": "2011", "author_list": "Zultanski, Susan L. and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/jxzew-6cq81", "eprint_id": 102853, "eprint_status": "archive", "datestamp": "2023-08-19 07:43:35", "lastmod": "2023-10-20 00:33:30", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Fujiwara-Yuji", "name": { "family": "Fujiwara", "given": "Yuji" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Application of a New Chiral Phosphepine to the Catalytic Asymmetric Synthesis of Highly Functionalized Cyclopentenes That Bear an Array of Heteroatom-Substituted Quaternary Stereocenters", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2011 American Chemical Society. \n\nReceived: May 27, 2011. Published: July 18, 2011. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM57034) and Dainippon Sumitomo Pharma Co., Ltd. (fellowship for Y.F.). We thank Dr. Jonathan E. Wilson for a preliminary study.\n\nAccepted Version - nihms312878.pdf
Supplemental Material - ja2049012_si_001.pdf
Supplemental Material - ja2049012_si_002.cif
Supplemental Material - ja2049012_si_003.cif
Supplemental Material - ja2049012_si_004.cif
Supplemental Material - ja2049012_si_005.cif
Supplemental Material - ja2049012_si_006.cif
", "abstract": "Through the design and synthesis of a new chiral phosphepine, the first catalytic asymmetric method for the [3 + 2] cycloaddition of allenes with olefins has been developed that generates cyclopentenes that bear nitrogen-, phosphorus-, oxygen-, and sulfur-substituted quaternary stereocenters. A wide array of racemic \u03b3-substituted allenes can be employed in this stereoconvergent process, which occurs with good enantioselectivity, diastereoselectivity, regioselectivity, and yield. Mechanistic studies, including a unique observation of a (modest) kinetic resolution of a racemic allene, are consistent with addition of the phosphepine to the allene being the turnover-limiting step of the catalytic cycle.", "date": "2011-08-10", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "133", "number": "31", "publisher": "American Chemical Society", "pagerange": "12293-12297", "id_number": "CaltechAUTHORS:20200428-095145770", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095145770", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM57034" }, { "agency": "Dainippon Sumitomo Pharma Co., Ltd." } ] }, "doi": "10.1021/ja2049012", "pmcid": "PMC3150361", "primary_object": { "basename": "nihms312878.pdf", "url": "https://authors.library.caltech.edu/records/jxzew-6cq81/files/nihms312878.pdf" }, "related_objects": [ { "basename": "ja2049012_si_001.pdf", "url": "https://authors.library.caltech.edu/records/jxzew-6cq81/files/ja2049012_si_001.pdf" }, { "basename": "ja2049012_si_002.cif", "url": "https://authors.library.caltech.edu/records/jxzew-6cq81/files/ja2049012_si_002.cif" }, { "basename": "ja2049012_si_003.cif", "url": "https://authors.library.caltech.edu/records/jxzew-6cq81/files/ja2049012_si_003.cif" }, { "basename": "ja2049012_si_004.cif", "url": "https://authors.library.caltech.edu/records/jxzew-6cq81/files/ja2049012_si_004.cif" }, { "basename": "ja2049012_si_005.cif", "url": "https://authors.library.caltech.edu/records/jxzew-6cq81/files/ja2049012_si_005.cif" }, { "basename": "ja2049012_si_006.cif", "url": "https://authors.library.caltech.edu/records/jxzew-6cq81/files/ja2049012_si_006.cif" } ], "resource_type": "article", "pub_year": "2011", "author_list": "Fujiwara, Yuji and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/tvdea-j9r35", "eprint_id": 102854, "eprint_status": "archive", "datestamp": "2023-08-22 02:54:17", "lastmod": "2023-10-20 00:33:33", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lu-Zhe", "name": { "family": "Lu", "given": "Zhe" } }, { "id": "Wilsily-A", "name": { "family": "Wilsily", "given": "Ashraf" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Stereoconvergent Amine-Directed Alkyl\u2013Alkyl Suzuki Reactions of Unactivated Secondary Alkyl Chlorides", "ispublished": "pub", "full_text_status": "public", "keywords": "Anions; Coupling reactions; Electrophiles'; Alkyls; Cross coupling reaction", "note": "\u00a9 2011 American Chemical Society. \n\nReceived: April 18, 2011. Published: May 10, 2011. \n\nThis study is dedicated to the memory of Prof. David Y. Gin. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM62871), Eli Lilly (fellowship to Z.L.), and the Martin Family Society of Fellows for Sustainability (fellowship to Z.L.).\n\nAccepted Version - nihms295619.pdf
Supplemental Material - ja203560q_si_001.pdf
", "abstract": "A new family of stereoconvergent cross-couplings of unactivated secondary alkyl electrophiles has been developed, specifically, arylamine-directed alkyl\u2013alkyl Suzuki reactions. This represents the first such investigation to be focused on the use of alkyl chlorides as substrates. Structure\u2013enantioselectivity studies are consistent with the nitrogen, not the aromatic ring, serving as the primary site of coordination of the arylamine to the catalyst. The rate law for this asymmetric cross-coupling is compatible with transmetalation being the turnover-limiting step of the catalytic cycle.", "date": "2011-06-01", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "133", "number": "21", "publisher": "American Chemical Society", "pagerange": "8154-8157", "id_number": "CaltechAUTHORS:20200428-095145872", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095145872", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Eli Lilly" }, { "agency": "Martin Family Society of Fellows for Sustainability" } ] }, "doi": "10.1021/ja203560q", "pmcid": "PMC3102136", "primary_object": { "basename": "nihms295619.pdf", "url": "https://authors.library.caltech.edu/records/tvdea-j9r35/files/nihms295619.pdf" }, "related_objects": [ { "basename": "ja203560q_si_001.pdf", "url": "https://authors.library.caltech.edu/records/tvdea-j9r35/files/ja203560q_si_001.pdf" } ], "resource_type": "article", "pub_year": "2011", "author_list": "Lu, Zhe; Wilsily, Ashraf; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/hr85k-1cp21", "eprint_id": 103068, "eprint_status": "archive", "datestamp": "2023-08-19 06:17:23", "lastmod": "2023-10-20 00:45:03", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Bachovchin-D-A", "name": { "family": "Bachovchin", "given": "Daniel A." } }, { "id": "Mohr-J-T", "name": { "family": "Mohr", "given": "Justin T." }, "orcid": "0000-0002-7005-3322" }, { "id": "Speers-A-E", "name": { "family": "Speers", "given": "Anna E." } }, { "id": "Wang-Chu", "name": { "family": "Wang", "given": "Chu" } }, { "id": "Berlin-J-M", "name": { "family": "Berlin", "given": "Jacob M." }, "orcid": "0000-0001-7498-766X" }, { "id": "Spicer-T-P", "name": { "family": "Spicer", "given": "Timothy P." } }, { "id": "Fernandez-Vega-Virneliz", "name": { "family": "Fernandez-Vega", "given": "Virneliz" } }, { "id": "Chase-Peter", "name": { "family": "Chase", "given": "Peter" } }, { "id": "Hodder-P-S", "name": { "family": "Hodder", "given": "Peter S." } }, { "id": "Sch\u00fcrer-S-C", "name": { "family": "Sch\u00fcrer", "given": "Stephan C." } }, { "id": "Nomura-Daniel-K", "name": { "family": "Nomura", "given": "Daniel K." } }, { "id": "Rosen-Hugh", "name": { "family": "Rosen", "given": "Hugh" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" }, { "id": "Cravatt-B-F", "name": { "family": "Cravatt", "given": "Benjamin F." } } ] }, "title": "Academic cross-fertilization by public screening yields a remarkable class of protein phosphatase methylesterase-1 inhibitors", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2011 National Academy of Sciences. \n\nEdited by Stuart L. Schreiber, Broad Institute, Cambridge, MA, and approved January 13, 2011 (received for review November 24, 2010). \n\nWe thank Tianyang Ji, David Milliken, Kim Masuda, Benjamin Kipper, and Jaclyn M. Murphy for technical assistance. This work was supported by National Institutes of Health grants CA132630 (B.F.C.), MH084512 (H.R.), GM57034 (G.C.F.), and GM086040 (postdoctoral fellowship to J.T.M.); the National Science Foundation (predoctoral fellowship to D.A.B.); the California Breast Cancer Research Program (predoctoral fellowship to D.A.B.); and The Skaggs Institute for Chemical Biology. \n\nAuthor contributions: D.A.B., J.T.M., H.R., G.C.F., and B.F.C. designed research; D.A.B., J.T.M., J.M.B., T.P.S., V.F.-V., P.C., P.S.H., S.C.S., and D.K.N. performed research; D.A.B., J.T.M., C.W., J.M.B., and S.C.S. contributed new reagents/analytic tools; D.A.B., J.T.M., A.E.S., C.W., T.P.S., P.S.H., S.C.S., H.R., G.C.F., and B.F.C. analyzed data; and D.A.B., J.T.M., A.E.S., H.R., G.C.F., and B.F.C. wrote the paper. \n\nThe authors declare no conflict of interest. \n\nThis article is a PNAS Direct Submission. \n\nThis article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1015248108/-/DCSupplemental.\n\nPublished - 6811.full.pdf
Supplemental Material - pnas.1015248108_SI.pdf
", "abstract": "National Institutes of Health (NIH)-sponsored screening centers provide academic researchers with a special opportunity to pursue small-molecule probes for protein targets that are outside the current interest of, or beyond the standard technologies employed by, the pharmaceutical industry. Here, we describe the outcome of an inhibitor screen for one such target, the enzyme protein phosphatase methylesterase-1 (PME-1), which regulates the methylesterification state of protein phosphatase 2A (PP2A) and is implicated in cancer and neurodegeneration. Inhibitors of PME-1 have not yet been described, which we attribute, at least in part, to a dearth of substrate assays compatible with high-throughput screening. We show that PME-1 is assayable by fluorescence polarization-activity-based protein profiling (fluopol-ABPP) and use this platform to screen the 300,000+ member NIH small-molecule library. This screen identified an unusual class of compounds, the aza-\u03b2-lactams (ABLs), as potent (IC\u2085\u2080 values of approximately 10 nM), covalent PME-1 inhibitors. Interestingly, ABLs did not derive from a commercial vendor but rather an academic contribution to the public library. We show using competitive-ABPP that ABLs are exquisitely selective for PME-1 in living cells and mice, where enzyme inactivation leads to substantial reductions in demethylated PP2A. In summary, we have combined advanced synthetic and chemoproteomic methods to discover a class of ABL inhibitors that can be used to selectively perturb PME-1 activity in diverse biological systems. More generally, these results illustrate how public screening centers can serve as hubs to create spontaneous collaborative opportunities between synthetic chemistry and chemical biology labs interested in creating first-in-class pharmacological probes for challenging protein targets.", "date": "2011-04-26", "date_type": "published", "publication": "Proceedings of the National Academy of Sciences of the United States of America", "volume": "108", "number": "17", "publisher": "National Academy of Sciences", "pagerange": "6811-6816", "id_number": "CaltechAUTHORS:20200507-105436538", "issn": "0027-8424", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200507-105436538", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "CA132630" }, { "agency": "NIH", "grant_number": "MH084512" }, { "agency": "NIH", "grant_number": "GM57034" }, { "agency": "NIH Postdoctoral Fellowship", "grant_number": "GM086040" }, { "agency": "NSF Graduate Research Fellowship" }, { "agency": "California Breast Cancer Research Program" }, { "agency": "Skaggs Institute for Chemical Biology" } ] }, "doi": "10.1073/pnas.1015248108", "pmcid": "PMC3084096", "primary_object": { "basename": "6811.full.pdf", "url": "https://authors.library.caltech.edu/records/hr85k-1cp21/files/6811.full.pdf" }, "related_objects": [ { "basename": "pnas.1015248108_SI.pdf", "url": "https://authors.library.caltech.edu/records/hr85k-1cp21/files/pnas.1015248108_SI.pdf" } ], "resource_type": "article", "pub_year": "2011", "author_list": "Bachovchin, Daniel A.; Mohr, Justin T.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/whgs9-zx298", "eprint_id": 103188, "eprint_status": "archive", "datestamp": "2023-08-19 04:29:36", "lastmod": "2023-10-20 15:45:11", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Sinisi-R", "name": { "family": "Sinisi", "given": "Riccardo" } }, { "id": "Sun-Jianwei", "name": { "family": "Sun", "given": "Jianwei" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Phosphine-catalyzed asymmetric additions of malonate esters to \u03b3-substituted allenoates and allenamides", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 National Academy of Sciences. \n\nEdited by David W. C. MacMillan, Princeton University, Princeton, NJ, and accepted by the Editorial Board May 30, 2010 (received for review March 18, 2010). PNAS first published July 12, 2010. \n\nWe thank Dr. Sean W. Smith for preliminary studies and Dr. Meiliana Tjandra and Shaun D. Fontaine for experimental assistance. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM57034), the University of Bologna (Marco Polo fellowship for R.S.), Merck Research Laboratories, and Novartis. \n\nR.S. and J.S. contributed equally to this work. \n\nAuthor contributions: R.S., J.S., and G.C.F. designed research; R.S. and J.S. performed research; R.S., J.S., and G.C.F. analyzed data; and J.S. and G.C.F. wrote the paper. \n\nThe authors declare no conflict of interest. \n\nThis article is a PNAS Direct Submission. D.W.M. is a guest editor invited by the Editorial Board. \n\nThis article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1003597107/-/DCSupplemental.\n\nPublished - 20652.full.pdf
Supplemental Material - Appendix.pdf
", "abstract": "Because carbonyl groups are ubiquitous in organic chemistry, the ability to synthesize functionalized carbonyl compounds, particularly enantioselectively, is an important objective. We have developed a straightforward and versatile method for catalytic asymmetric carbon\u2013carbon bond formation at the \u03b3-position of carbonyl compounds, specifically, phosphine-catalyzed additions of malonate esters to \u03b3-substituted allenoates and allenamides. Mechanistic studies have provided insight into the reaction pathway.", "date": "2010-11-30", "date_type": "published", "publication": "Proceedings of the National Academy of Sciences of the United States of America", "volume": "107", "number": "48", "publisher": "National Academy of Sciences", "pagerange": "20652-20654", "id_number": "CaltechAUTHORS:20200513-150749013", "issn": "0027-8424", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200513-150749013", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM57034" }, { "agency": "University of Bologna" }, { "agency": "Merck Research Laboratories" }, { "agency": "Novartis" } ] }, "doi": "10.1073/pnas.1003597107", "pmcid": "PMC2996437", "primary_object": { "basename": "20652.full.pdf", "url": "https://authors.library.caltech.edu/records/whgs9-zx298/files/20652.full.pdf" }, "related_objects": [ { "basename": "Appendix.pdf", "url": "https://authors.library.caltech.edu/records/whgs9-zx298/files/Appendix.pdf" } ], "resource_type": "article", "pub_year": "2010", "author_list": "Sinisi, Riccardo; Sun, Jianwei; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/4s7t0-2wx50", "eprint_id": 103170, "eprint_status": "archive", "datestamp": "2023-08-22 01:06:58", "lastmod": "2023-10-20 15:43:55", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lou-Sha", "name": { "family": "Lou", "given": "Sha" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Palladium/Tris(tert-butyl)phosphine\u2010Catalyzed Suzuki Cross\u2010 Couplings in the Presence of Water", "ispublished": "pub", "full_text_status": "public", "keywords": "boron; cross-coupling; halides; palladium; water", "note": "\u00a9 2010 Wiley\u2010VCH Verlag GmbH & Co. KGaA, Weinheim. \n\nReceived: April 5, 2010; Published online: July 21, 2010. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, grant R01\u2010GM62871), Merck Research Laboratories, and Novartis. We thank Dr. Xing Dai for a preliminary study.\n\nAccepted Version - nihms257833.pdf
Supplemental Material - adsc_201000267_sm_miscellaneous_information.pdf
", "abstract": "Dipalladiumtris(dibenzylideneacetone)/tris(tert\u2010butyl)phosphonium tetrafluoroborate/potassium fluoride dihydrate [Pd\u2082(dba)\u2083/[HP(t\u2010Bu)\u2083]BF\u2084/KF\u22c52\u2009H\u2082O] serves as a mild, robust, and user\u2010friendly method for the efficient Suzuki cross\u2010coupling of a diverse array of aryl and heteroaryl halides with aryl\u2010 and heteroarylboronic acids.", "date": "2010-10-09", "date_type": "published", "publication": "Advanced Synthesis and Catalysis", "volume": "352", "number": "11\u201012", "publisher": "Wiley", "pagerange": "2081-2084", "id_number": "CaltechAUTHORS:20200513-095516372", "issn": "1615-4150", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200513-095516372", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01\u2010GM62871" }, { "agency": "Merck Research Laboratories" }, { "agency": "Novartis" } ] }, "doi": "10.1002/adsc.201000267", "pmcid": "PMC3011868", "primary_object": { "basename": "adsc_201000267_sm_miscellaneous_information.pdf", "url": "https://authors.library.caltech.edu/records/4s7t0-2wx50/files/adsc_201000267_sm_miscellaneous_information.pdf" }, "related_objects": [ { "basename": "nihms257833.pdf", "url": "https://authors.library.caltech.edu/records/4s7t0-2wx50/files/nihms257833.pdf" } ], "resource_type": "article", "pub_year": "2010", "author_list": "Lou, Sha and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/jvx74-46e24", "eprint_id": 103171, "eprint_status": "archive", "datestamp": "2023-08-22 00:48:58", "lastmod": "2023-10-20 15:43:58", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lu-Zhe", "name": { "family": "Lu", "given": "Zhe" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Alkyl-Alkyl Suzuki Cross-Coupling of Unactivated Secondary Alkyl Chlorides", "ispublished": "pub", "full_text_status": "public", "keywords": "alkyl halides; boron; cross\u2010coupling; homogeneous catalysis; nickel", "note": "\u00a9 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. \n\nReceived: May 30, 2010; Published online: August 16, 2010. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, grant R01-GM62871), Eli Lilly (fellowship to Z.L.), the Martin Family Society of Fellows for Sustainability (fellowship to Z.L.), Merck Research Laboratories, and Novartis. We thank Dr. Bunnai Saito for preliminary studies and Dr. Jeffrey H. Simpson for assistance with NMR spectroscopy.\n\nAccepted Version - nihms257830.pdf
Supplemental Material - anie_201003272_sm_miscellaneous_information.pdf
", "abstract": "No such thing as a problem substrate! In a reaction designed specifically for the title substrates C-C coupling with alkyl boranes occurred in good yield at room temperature with commercially available catalyst components (see scheme). This versatile method is also suitable for Suzuki reactions of secondary and primary alkyl bromides and iodides, as well as primary alkyl chlorides.", "date": "2010-09-03", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "49", "number": "37", "publisher": "Wiley", "pagerange": "6676-6678", "id_number": "CaltechAUTHORS:20200513-100146935", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200513-100146935", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Eli Lilly" }, { "agency": "Martin Family Society of Fellows for Sustainability" }, { "agency": "Merck Research Laboratories" }, { "agency": "Novartis" } ] }, "doi": "10.1002/anie.201003272", "pmcid": "PMC3073318", "primary_object": { "basename": "anie_201003272_sm_miscellaneous_information.pdf", "url": "https://authors.library.caltech.edu/records/jvx74-46e24/files/anie_201003272_sm_miscellaneous_information.pdf" }, "related_objects": [ { "basename": "nihms257830.pdf", "url": "https://authors.library.caltech.edu/records/jvx74-46e24/files/nihms257830.pdf" } ], "resource_type": "article", "pub_year": "2010", "author_list": "Lu, Zhe and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/tbs1n-96c33", "eprint_id": 102858, "eprint_status": "archive", "datestamp": "2023-08-19 03:45:01", "lastmod": "2023-10-20 00:33:46", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Owston-N-A", "name": { "family": "Owston", "given": "Nathan A." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Asymmetric Alkyl\u2212Alkyl Cross-Couplings of Unactivated Secondary Alkyl Electrophiles: Stereoconvergent Suzuki Reactions of Racemic Acylated Halohydrins", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society. \n\nReceived July 5, 2010. \n\nWe thank Angelika Bruckmann for preliminary studies. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM62871).\n\nAccepted Version - nihms228431.pdf
Supplemental Material - ja105924f_si_001.pdf
", "abstract": "A method for asymmetric alkyl\u2212alkyl Suzuki reactions of unactivated secondary alkyl electrophiles, specifically, cross-couplings of racemic acylated halohydrins with alkylborane reagents, has been developed. A range of protected bromohydrins, as well as a protected chlorohydrin and a homologated bromohydrin, are coupled in good ee by a catalyst derived from commercially available components.", "date": "2010-09-01", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "132", "number": "34", "publisher": "American Chemical Society", "pagerange": "11908-11909", "id_number": "CaltechAUTHORS:20200428-095146269", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095146269", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" } ] }, "doi": "10.1021/ja105924f", "pmcid": "PMC2929007", "primary_object": { "basename": "ja105924f_si_001.pdf", "url": "https://authors.library.caltech.edu/records/tbs1n-96c33/files/ja105924f_si_001.pdf" }, "related_objects": [ { "basename": "nihms228431.pdf", "url": "https://authors.library.caltech.edu/records/tbs1n-96c33/files/nihms228431.pdf" } ], "resource_type": "article", "pub_year": "2010", "author_list": "Owston, Nathan A. and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/tvxf2-phm23", "eprint_id": 102859, "eprint_status": "archive", "datestamp": "2023-08-19 03:34:21", "lastmod": "2023-10-20 00:33:53", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lundin-P-M", "name": { "family": "Lundin", "given": "Pamela M." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Asymmetric Suzuki Cross-Couplings of Activated Secondary Alkyl Electrophiles: Arylations of Racemic \u03b1-Chloroamides", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society. \n\nReceived June 12, 2010. \n\nWe thank Dr. Francisco Gonz\u00e1lez-Bobes for preliminary studies. Support was provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM62871), Eli Lilly (fellowship to P.M.L.), Novartis (fellowship to P.M.L.), and the Merck Research Laboratories.\n\nAccepted Version - nihms225483.pdf
Supplemental Material - ja105148g_si_001.pdf
", "abstract": "A nickel-catalyzed stereoconvergent method for the enantioselective Suzuki arylation of racemic \u03b1-chloroamides has been developed. This process provides a unique example of an asymmetric arylation of an \u03b1-haloamide, an enantioselective arylation of an \u03b1-chlorocarbonyl compound, and an asymmetric Suzuki reaction with an activated alkyl electrophile or an arylboron reagent. The method is also applicable to the corresponding enantioselective cross-coupling of \u03b1-bromoamides. The coupling products can be transformed without racemization into enantioenriched \u03b1-arylcarboxylic acids and primary alcohols. A modest kinetic resolution of the \u03b1-chloroamide was observed; a mechanistic study indicated that the selectivity may reflect discrimination by the chiral catalyst of the two enantiomeric \u03b1-chloroamides in an irreversible oxidative-addition process.", "date": "2010-08-18", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "132", "number": "32", "publisher": "American Chemical Society", "pagerange": "11027-11029", "id_number": "CaltechAUTHORS:20200428-095146364", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095146364", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Eli Lilly" }, { "agency": "Novartis" }, { "agency": "Merck Research Laboratories" } ] }, "doi": "10.1021/ja105148g", "pmcid": "PMC2924160", "primary_object": { "basename": "ja105148g_si_001.pdf", "url": "https://authors.library.caltech.edu/records/tvxf2-phm23/files/ja105148g_si_001.pdf" }, "related_objects": [ { "basename": "nihms225483.pdf", "url": "https://authors.library.caltech.edu/records/tvxf2-phm23/files/nihms225483.pdf" } ], "resource_type": "article", "pub_year": "2010", "author_list": "Lundin, Pamela M. and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/qeh2t-ym175", "eprint_id": 102860, "eprint_status": "archive", "datestamp": "2023-08-19 02:12:52", "lastmod": "2023-10-20 00:33:57", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lou-Sha", "name": { "family": "Lou", "given": "Sha" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Enantioselective Alkenylation via Nickel-Catalyzed Cross-Coupling with Organozirconium Reagents", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society. \n\nReceived February 28, 2010. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM62871), Merck Research Laboratories, and Novartis. We thank Shaun D. Fontaine, Dr. Peter Mueller, and Dr. Michael R. Reithofer for assistance.\n\nAccepted Version - nihms189896.pdf
Supplemental Material - ja1017046_si_001.cif
Supplemental Material - ja1017046_si_002.pdf
", "abstract": "A new family of organometallic compounds, organozirconium reagents, are shown to serve as suitable partners in cross-coupling reactions of (activated) secondary alkyl electrophiles. Thus, the first catalytic method for coupling secondary \u03b1-bromoketones with alkenylmetal reagents has been developed, specifically, a mild, versatile, and stereoconvergent carbon\u2212carbon bond-forming process that generates potentially labile \u03b2,\u03b3-unsaturated ketones with good enantioselectivity.", "date": "2010-04-14", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "132", "number": "14", "publisher": "American Chemical Society", "pagerange": "5010-5011", "id_number": "CaltechAUTHORS:20200428-095146456", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095146456", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Merck Research Laboratories" }, { "agency": "Novartis" } ] }, "collection": "CaltechAUTHORS", "doi": "10.1021/ja1017046", "pmcid": "PMC2860276", "primary_object": { "basename": "ja1017046_si_001.cif", "url": "https://authors.library.caltech.edu/records/qeh2t-ym175/files/ja1017046_si_001.cif" }, "related_objects": [ { "basename": "ja1017046_si_002.pdf", "url": "https://authors.library.caltech.edu/records/qeh2t-ym175/files/ja1017046_si_002.pdf" }, { "basename": "nihms189896.pdf", "url": "https://authors.library.caltech.edu/records/qeh2t-ym175/files/nihms189896.pdf" } ], "resource_type": "article", "pub_year": "2010", "author_list": "Lou, Sha and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/hdw7x-tty02", "eprint_id": 102861, "eprint_status": "archive", "datestamp": "2023-08-19 02:11:34", "lastmod": "2023-10-20 00:34:21", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Sun-Jianwei", "name": { "family": "Sun", "given": "Jianwei" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Phosphine-Catalyzed Formation of Carbon\u2212Sulfur Bonds: Catalytic Asymmetric Synthesis of \u03b3-Thioesters", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society. \n\nReceived 11 February 2010. Published online1 1 March 2010. \n\nSupport was provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM57034), Merck, and Novartis. We thank Dr. Ying Kit Chung for preliminary studies.\n\nAccepted Version - nihms187016.pdf
Supplemental Material - ja101251d_si_001.pdf
Supplemental Material - ja101251d_si_002.cif
", "abstract": "A method for catalytic asymmetric \u03b3 sulfenylation of carbonyl compounds has been developed. In the presence of an appropriate catalyst, thiols not only add to the \u03b3 position of allenoates, overcoming their propensity to add to the \u03b2 position in the absence of a catalyst, but do so with very good enantioselectivity. Sulfur nucleophiles are now added to the three families of nucleophiles (carbon, nitrogen, and oxygen) that had earlier been shown to participate in catalyzed \u03b3 additions. The phosphine catalyst of choice, TangPhos, had previously only been employed as a chiral ligand for transition metals, not as an efficient enantioselective nucleophilic catalyst.", "date": "2010-04-07", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "132", "number": "13", "publisher": "American Chemical Society", "pagerange": "4568-4569", "id_number": "CaltechAUTHORS:20200428-095146544", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095146544", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM57034" }, { "agency": "Merck Research Laboratories" }, { "agency": "Novartis" } ] }, "collection": "CaltechAUTHORS", "doi": "10.1021/ja101251d", "pmcid": "PMC2850260", "primary_object": { "basename": "ja101251d_si_002.cif", "url": "https://authors.library.caltech.edu/records/hdw7x-tty02/files/ja101251d_si_002.cif" }, "related_objects": [ { "basename": "ja101251d_si_001.pdf", "url": "https://authors.library.caltech.edu/records/hdw7x-tty02/files/ja101251d_si_001.pdf" }, { "basename": "nihms187016.pdf", "url": "https://authors.library.caltech.edu/records/hdw7x-tty02/files/nihms187016.pdf" } ], "resource_type": "article", "pub_year": "2010", "author_list": "Sun, Jianwei and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/8je6x-kp752", "eprint_id": 102862, "eprint_status": "archive", "datestamp": "2023-08-19 01:36:05", "lastmod": "2023-10-20 00:34:26", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lou-Sha", "name": { "family": "Lou", "given": "Sha" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Nickel/Bis(oxazoline)-Catalyzed Asymmetric Kumada Reactions of Alkyl Electrophiles: Cross-Couplings of Racemic \u03b1-Bromoketones", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 American Chemical Society. \n\nReceived 15 November 2009. Published online 5 January 2010. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM62871), Merck Research Laboratories, and Novartis. We thank Pamela M. Lundin and Koyel X. Bhattacharyya for preliminary studies.\n\nAccepted Version - nihms-168880.pdf
Supplemental Material - ja909689t_si_001.cif
Supplemental Material - ja909689t_si_002.pdf
", "abstract": "The first asymmetric Kumada reactions of alkyl electrophiles are described, specifically, cross-couplings of racemic \u03b1-bromoketones with aryl Grignard reagents. Several features of this investigation are of interest. First, the couplings proceed at remarkably low temperature (\u221240 or \u221260 \u00b0C), which enables the asymmetric synthesis of racemization-prone \u03b1-arylketones. Second, dialkyl ketones undergo enantioselective coupling in good ee and yield. Third, readily available bis(oxazolines) are shown for the first time to be effective ligands for cross-couplings of alkyl electrophiles, thereby opening the door to new opportunities in asymmetric catalysis.", "date": "2010-02-03", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "132", "number": "4", "publisher": "American Chemical Society", "pagerange": "1264-1266", "id_number": "CaltechAUTHORS:20200428-095146636", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095146636", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Merck Research Laboratories" }, { "agency": "Novartis" } ] }, "doi": "10.1021/ja909689t", "pmcid": "PMC2814537", "primary_object": { "basename": "ja909689t_si_001.cif", "url": "https://authors.library.caltech.edu/records/8je6x-kp752/files/ja909689t_si_001.cif" }, "related_objects": [ { "basename": "ja909689t_si_002.pdf", "url": "https://authors.library.caltech.edu/records/8je6x-kp752/files/ja909689t_si_002.pdf" }, { "basename": "nihms-168880.pdf", "url": "https://authors.library.caltech.edu/records/8je6x-kp752/files/nihms-168880.pdf" } ], "resource_type": "article", "pub_year": "2010", "author_list": "Lou, Sha and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/sghc8-4hc57", "eprint_id": 102910, "eprint_status": "archive", "datestamp": "2023-09-21 23:20:51", "lastmod": "2023-10-23 23:21:31", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Wilson-J-E", "name": { "family": "Wilson", "given": "Jonathan\u2005E." } }, { "id": "Sun-Jianwei", "name": { "family": "Sun", "given": "Jianwei" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Stereoselective Phosphine-Catalyzed Synthesis of Highly Functionalized Diquinanes", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010 WILEY\u2010VCH Verlag GmbH & Co. \n\nReceived: September 12, 2009. Published online: November 26, 2009. \n\nThis work has been supported by the National Institutes of Health (National Institute of General Medical Sciences, R01\u2010GM57034), Merck Research Laboratories, Novartis, and Boehringer Ingelheim. We thank Evonik for a gift of phosphepine 3 and Dr. Jeffrey\u2005H. Simpson (MIT) for assistance with NMR studies.\n\nSupplemental Material - downloadSupplement_doi=10.1002_2Fanie.200905125_file=anie_200905125_sm_miscellaneous_information.pdf
", "abstract": "Two rings to rule them all: A versatile method has been developed for the room\u2010temperature synthesis of diquinanes from acyclic precursors, thereby generating two rings, three stereocenters, and a double bond with high selectivity. The products of the double cyclization can be derivatized with excellent diastereoselection into an array of highly functionalized compounds.\n\n[reaction image]\n\nIn 2003, Tomika and co\u2010workers reported an intriguing PnBu3\u2010catalyzed diastereoselective cyclization of certain yne\u2010diones to form bicyclic furanones with two new stereocenters (Figure\u20051).1 They proposed that conjugate addition of the phosphine to the alkyne is followed by tautomerization, which furnishes zwitterionic enolate A. Next, an intramolecular aldol reaction provides B, and then a second conjugate addition generates bicycle C (the conversion of A into C by a concerted cycloaddition may also be considered). Tautomerization and then elimination of the phosphine affords the bicyclic furanone. The investigation by Tomita et al. focused mainly on symmetrical substrates (R1=-C\u2261CR), although they did report reactions of two unsymmetrical yne\u2010diones which cyclized in relatively modest yield (41\u201350\u2009%).", "date": "2010-01-04", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "49", "number": "1", "publisher": "Wiley", "pagerange": "161-163", "id_number": "CaltechAUTHORS:20200429-135023160", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200429-135023160", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01\u2010GM57034" }, { "agency": "Merck Research Laboratories" }, { "agency": "Novartis" }, { "agency": "Boehringer-Ingelheim" } ] }, "doi": "10.1002/anie.200905125", "primary_object": { "basename": "10.1002:anie.200905125-SI.pdf", "url": "https://authors.library.caltech.edu/records/sghc8-4hc57/files/10.1002:anie.200905125-SI.pdf" }, "resource_type": "article", "pub_year": "2010", "author_list": "Wilson, Jonathan\u2005E.; Sun, Jianwei; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/k0jmm-89363", "eprint_id": 102864, "eprint_status": "archive", "datestamp": "2023-08-19 01:12:16", "lastmod": "2023-10-20 00:34:33", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lou-Sha", "name": { "family": "Lou", "given": "Sha" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Nickel-catalyzed asymmetric Negishi cross-couplings of racemic secondary allylic chlorides with alkylzincs: (S,E)-ethyl 6-(1,3-dioxolan-2-yl)-4-methylhex-2-enoate", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010, Organic Syntheses, Inc.\n\nAccepted Version - nihms257825.pdf
", "abstract": "[no abstract]", "date": "2010", "date_type": "published", "publication": "Organic Syntheses", "volume": "87", "publisher": "Organic Syntheses, Inc.", "pagerange": "317-329", "id_number": "CaltechAUTHORS:20200428-095146819", "issn": "0078-6209", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095146819", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "doi": "10.15227/orgsyn.087.0317", "pmcid": "PMC3100190", "primary_object": { "basename": "nihms257825.pdf", "url": "https://authors.library.caltech.edu/records/k0jmm-89363/files/nihms257825.pdf" }, "resource_type": "article", "pub_year": "2010", "author_list": "Lou, Sha and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/p2cd9-dyz42", "eprint_id": 102865, "eprint_status": "archive", "datestamp": "2023-08-19 01:12:25", "lastmod": "2023-10-20 00:34:39", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lou-Sha", "name": { "family": "Lou", "given": "Sha" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Nickel-catalyzed enantioselective Negishi cross-couplings of racemic secondary \u03b1-bromo amides with alkylzinc reagents: (s)-N-benzyl-7-cyano-2-ethyl-N-phenylheptanamide", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010, Organic Syntheses, Inc.\n\nAccepted Version - nihms257828.pdf
", "abstract": "[no abstract]", "date": "2010", "date_type": "published", "publication": "Organic Syntheses", "volume": "87", "publisher": "Organic Syntheses, Inc.", "pagerange": "330-338", "id_number": "CaltechAUTHORS:20200428-095146913", "issn": "0078-6209", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095146913", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "doi": "10.15227/orgsyn.087.0330", "pmcid": "PMC3083032", "primary_object": { "basename": "nihms257828.pdf", "url": "https://authors.library.caltech.edu/records/p2cd9-dyz42/files/nihms257828.pdf" }, "resource_type": "article", "pub_year": "2010", "author_list": "Lou, Sha and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/j75n7-4cy79", "eprint_id": 102866, "eprint_status": "archive", "datestamp": "2023-08-19 01:12:34", "lastmod": "2023-10-20 00:34:43", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lou-Sha", "name": { "family": "Lou", "given": "Sha" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Palladium-catalyzed alkyl-alkyl Suzuki cross-coupling of primary alkyl bromides at room temperature: (13-cholorotridecyloxy)triethylsilane", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010, Organic Syntheses, Inc. \n\nSubmitted by Sha Lou and Gregory C. Fu. Checked by Takuya Higo and Tohru Fukuyama.\n\nAccepted Version - nihms-257832.pdf
", "abstract": "[no abstract]", "date": "2010", "date_type": "published", "publication": "Organic Syntheses", "volume": "87", "publisher": "Organic Syntheses, Inc.", "pagerange": "299-309", "id_number": "CaltechAUTHORS:20200428-095146994", "issn": "0078-6209", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095146994", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "doi": "10.15227/orgsyn.087.0299", "pmcid": "PMC3008580", "primary_object": { "basename": "nihms-257832.pdf", "url": "https://authors.library.caltech.edu/records/j75n7-4cy79/files/nihms-257832.pdf" }, "resource_type": "article", "pub_year": "2010", "author_list": "Lou, Sha and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/7208f-b0s07", "eprint_id": 102863, "eprint_status": "archive", "datestamp": "2023-08-19 01:12:07", "lastmod": "2023-10-20 00:34:31", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lou-Sha", "name": { "family": "Lou", "given": "Sha" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Synthesis of chiral pyridine bis(oxazoline) ligands for nickel-catalyzed asymmetric Negishi cross-couplings of secondary allylic chlorides with alkylzincs: 2,6-bis[(4R)-4,5-dihydro-4-(2-phenylethyl)-2-oxazolyl]-pyridine", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2010, Organic Syntheses, Inc. \n\nSubmitted by Sha Lou and Gregory C. Fu.\nChecked by Gavin Chit Tsui, David I. Chai, and Mark Lautens.\n\nAccepted Version - nihms-257797.pdf
", "abstract": "[no abstract]", "date": "2010", "date_type": "published", "publication": "Organic Syntheses", "volume": "87", "publisher": "Wiley", "pagerange": "310-316", "id_number": "CaltechAUTHORS:20200428-095146731", "issn": "0078-6209", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095146731", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "doi": "10.15227/orgsyn.087.0310", "pmcid": "PMC3100209", "primary_object": { "basename": "nihms-257797.pdf", "url": "https://authors.library.caltech.edu/records/7208f-b0s07/files/nihms-257797.pdf" }, "resource_type": "article", "pub_year": "2010", "author_list": "Lou, Sha and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/ceznh-x5a58", "eprint_id": 102867, "eprint_status": "archive", "datestamp": "2023-08-21 22:31:39", "lastmod": "2023-10-20 00:34:47", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Smith-Sean-W", "name": { "family": "Smith", "given": "Sean W." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Asymmetric Carbon\u2212Carbon Bond Formation \u03b3 to a Carbonyl Group: Phosphine-Catalyzed Addition of Nitromethane to Allenes", "ispublished": "pub", "full_text_status": "public", "keywords": "Functionalization; Hydrocarbons; Allenes; Substitution reactions; Catalysts", "note": "\u00a9 2009 American Chemical Society. \n\nReceived August 4, 2009. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM57034), Merck Research Laboratories, and Novartis. We thank Dr. Nicolas Marion for assistance, Evonik Degussa for providing samples of phosphepines 1\u22124, and Prof. Qi-Lin Zhou for providing a precursor to phosphine 5. Funding for the MIT Department of Chemistry Instrumentation Facility has been furnished in part by NIH IS10RR13886 and NSF DBI-9729592.\n\nAccepted Version - nihms147483.pdf
Supplemental Material - ja9061823_si_001.pdf
", "abstract": "A chiral phosphine catalyzes the addition of a carbon nucleophile to the \u03b3 position of an electron-poor allene (amide-, ester-, or phosphonate-substituted), in preference to isomerization to a 1,3-diene, in good ee and yield. This strategy provides an attractive method for the catalytic asymmetric \u03b3 functionalization of carbonyl (and related) compounds.", "date": "2009-10-14", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "131", "number": "40", "publisher": "American Chemical Society", "pagerange": "14231-14233", "id_number": "CaltechAUTHORS:20200428-095147086", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200428-095147086", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM57034" }, { "agency": "Merck Research Laboratories" }, { "agency": "Novartis" }, { "agency": "NIH", "grant_number": "IS10RR13886" }, { "agency": "NSF", "grant_number": "DBI-9729592" } ] }, "doi": "10.1021/ja9061823", "pmcid": "PMC2758928", "primary_object": { "basename": "ja9061823_si_001.pdf", "url": "https://authors.library.caltech.edu/records/ceznh-x5a58/files/ja9061823_si_001.pdf" }, "related_objects": [ { "basename": "nihms147483.pdf", "url": "https://authors.library.caltech.edu/records/ceznh-x5a58/files/nihms147483.pdf" } ], "resource_type": "article", "pub_year": "2009", "author_list": "Smith, Sean W. and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/kfj4b-9mx91", "eprint_id": 103260, "eprint_status": "archive", "datestamp": "2023-08-21 21:02:46", "lastmod": "2023-10-20 15:50:47", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Dochnahl-M", "name": { "family": "Dochnahl", "given": "Maximilian" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Catalytic Asymmetric Cycloaddition of Ketenes and Nitroso Compounds: Enantioselective Synthesis of \u03b1-Hydroxycarboxylic Acid Derivatives", "ispublished": "pub", "full_text_status": "public", "keywords": "asymmetric catalysis; carboxylic acids; cycloaddition; heterocycles; ketenes", "note": "\u00a9 2009 Wiley\u2010VCH Verlag GmbH & Co. KGaA, Weinheim. \n\nReceived: November 28, 2008; Published online: February 16, 2009. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, grant R01-GM57034), the German Academic Exchange Service (postdoctoral fellowship for M.D.), Merck Research Laboratories, and Novartis.\n\nAccepted Version - nihms-102360.pdf
Supplemental Material - anie_200805805_sm_miscellaneous_information.pdf
", "abstract": "The appropriate choice of chiral catalyst and starting materials leads to the synthesis of 1,2\u2010oxazetidin\u20103\u2010ones by cycloadditions of ketenes with nitroso compounds with very good regioselectivity and enantioselectivity. In addition to serving as potentially bioactive target molecules, the products can be transformed into other important classes of compounds, such as \u03b1\u2010hydroxycarboxylic acid derivatives.", "date": "2009-03-16", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "48", "number": "13", "publisher": "Wiley", "pagerange": "2391-2393", "id_number": "CaltechAUTHORS:20200518-080028686", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200518-080028686", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM57034" }, { "agency": "Deutscher Akademischer Austauschdienst (DAAD)" }, { "agency": "Merck Research Laboratories" }, { "agency": "Novartis" } ] }, "doi": "10.1002/anie.200805805", "pmcid": "PMC2728616", "primary_object": { "basename": "anie_200805805_sm_miscellaneous_information.pdf", "url": "https://authors.library.caltech.edu/records/kfj4b-9mx91/files/anie_200805805_sm_miscellaneous_information.pdf" }, "related_objects": [ { "basename": "nihms-102360.pdf", "url": "https://authors.library.caltech.edu/records/kfj4b-9mx91/files/nihms-102360.pdf" } ], "resource_type": "article", "pub_year": "2009", "author_list": "Dochnahl, Maximilian and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/1w740-x6b73", "eprint_id": 104088, "eprint_status": "archive", "datestamp": "2023-08-20 01:09:49", "lastmod": "2023-10-20 19:04:20", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Chung-Ying-Kit", "name": { "family": "Chung", "given": "Ying\u2005Kit" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Phosphine-Catalyzed Enantioselective Synthesis of Oxygen Heterocycles", "ispublished": "pub", "full_text_status": "public", "keywords": "asymmetric catalysis \u00b7 cyclization \u00b7 isomerization \u00b7 oxygen heterocycles \u00b7 phosphanes", "note": "\u00a9 2009 WILEY\u2010VCH. \n\nReceived: November 3, 2008. Published online: February 11, 2009. \n\nWe thank Prof. Qi\u2010Lin Zhou, Kodak, and Degussa for generous gifts of catalysts and catalyst precursors. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences, grant R01\u2010GM57034), the Croucher Foundation (postdoctoral fellowship for Y.K.C.), Merck Research Laboratories, and Novartis.\n\nAccepted Version - nihms-102361.pdf
Supplemental Material - anie_200805377_sm_miscellaneous_information.pdf
", "abstract": "Chiral phosphepine 1 catalyzes the transformation of an array of hydroxy\u20102\u2010alkynoates into saturated oxygen heterocycles with good enantioselectivity. Phenols are also shown to participate in such phosphine\u2010catalyzed cyclizations, including an asymmetric variant. This method provides a new approach to the enantioselective synthesis of tetrahydrofurans, tetrahydropyrans, and dihydrobenzopyrans.", "date": "2009-03-09", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "48", "number": "12", "publisher": "Wiley", "pagerange": "2225-2227", "id_number": "CaltechAUTHORS:20200626-123754806", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200626-123754806", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01\u2010GM57034" }, { "agency": "Croucher Foundation" }, { "agency": "Merck Research Laboratories" }, { "agency": "Novartis" } ] }, "doi": "10.1002/anie.200805377", "pmcid": "PMC2747790", "primary_object": { "basename": "anie_200805377_sm_miscellaneous_information.pdf", "url": "https://authors.library.caltech.edu/records/1w740-x6b73/files/anie_200805377_sm_miscellaneous_information.pdf" }, "related_objects": [ { "basename": "nihms-102361.pdf", "url": "https://authors.library.caltech.edu/records/1w740-x6b73/files/nihms-102361.pdf" } ], "resource_type": "article", "pub_year": "2009", "author_list": "Chung, Ying\u2005Kit and Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/jg8st-1gn95", "eprint_id": 104087, "eprint_status": "archive", "datestamp": "2023-08-20 00:14:49", "lastmod": "2023-10-20 19:04:17", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Lundin-P-M", "name": { "family": "Lundin", "given": "Pamela\u2005M." } }, { "id": "Esquivias-Jorge", "name": { "family": "Esquivias", "given": "Jorge" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Catalytic Asymmetric Cross-Couplings of Racemic \u03b1-Bromoketones with Arylzinc Reagents", "ispublished": "pub", "full_text_status": "public", "keywords": "asymmetric catalysis \u00b7 enantioselectivity \u00b7 ketones \u00b7 nickel \u00b7 zinc", "note": "\u00a9 2009 WILEY\u2010VCH. \n\nReceived: October 6, 2008. Published online: November 28, 2008. \n\nSupport has been provided by the National Institutes of Health (National Institute of General Medical Sciences, grant R01\u2010GM62871), Merck Research Laboratories, Novartis, and the Spanish Department of Science (fellowship for J.E.).\n\nAccepted Version - nihms100112.pdf
Supplemental Material - anie_200804888_sm_miscellaneous_information.pdf
", "abstract": "Nickel box : The first catalytic asymmetric method for cross\u2010coupling arylzinc reagents with \u03b1\u2010bromoketones has been developed (see scheme). This stereoconvergent carbon\u2013carbon bond\u2010forming process occurs under unusually mild conditions and without activators, thereby allowing the generation of potentially labile tertiary stereocenters.", "date": "2008-12-22", "date_type": "published", "publication": "Angewandte Chemie International Edition", "volume": "48", "number": "1", "publisher": "Wiley", "pagerange": "154-156", "id_number": "CaltechAUTHORS:20200626-123754710", "issn": "1433-7851", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200626-123754710", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01\u2010GM62871" }, { "agency": "Merck Research Laboratories" }, { "agency": "Novartis" }, { "agency": "Ministerio de Ciencia e Innovaci\u00f3n (MCINN)" } ] }, "doi": "10.1002/anie.200804888", "pmcid": "PMC2790061", "primary_object": { "basename": "nihms100112.pdf", "url": "https://authors.library.caltech.edu/records/jg8st-1gn95/files/nihms100112.pdf" }, "related_objects": [ { "basename": "anie_200804888_sm_miscellaneous_information.pdf", "url": "https://authors.library.caltech.edu/records/jg8st-1gn95/files/anie_200804888_sm_miscellaneous_information.pdf" } ], "resource_type": "article", "pub_year": "2008", "author_list": "Lundin, Pamela\u2005M.; Esquivias, Jorge; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/najr5-qdn45", "eprint_id": 104086, "eprint_status": "archive", "datestamp": "2023-08-19 23:57:23", "lastmod": "2023-10-20 19:04:11", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "The Development of Versatile Methods for Palladium-Catalyzed Coupling Reactions of Aryl Electrophiles through the Use of P(t-Bu)\u2083 and PCy\u2083 as Ligands", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 2008 American Chemical Society. \n\nReceived 24 June 2008. Published online 24 October 2008. Published in issue 18 November 2008. \n\nThis article is part of the Cross Coupling special issue. \n\nI am extremely grateful to the co-workers who contributed to this program, particularly Adam F. Littke, who initiated our studies. Primary support for this investigation has been provided by the National Institutes of Health (National Institute of General Medical Sciences, Grant R01-GM62871), with supplementary funding furnished by Merck Research Laboratories and by Novartis. I thank Prof. Amir Hoveyda (Boston College) and Prof. Alan Sellinger (Institute of Materials Research & Engineering) for assistance with two of the illustrations.\n\nAccepted Version - nihms-86549.pdf
", "abstract": "Metal-catalyzed coupling reactions of aryl electrophiles with organometallics and with olefins serve as unusually effective tools for forming new carbon\u2212carbon bonds. By 1998, researchers had developed catalysts that achieved reactions of aryl iodides, bromides, and triflates. Nevertheless, many noteworthy challenges remained; among them were couplings of aryl iodides, bromides, and triflates under mild conditions (at room temperature, for example), couplings of hindered reaction partners, and couplings of inexpensive aryl chlorides. \n\nThis Account highlights some of the progress that has been made in our laboratory over the past decade, largely through the appropriate choice of ligand, in achieving these synthetic objectives. In particular, we have established that palladium in combination with a bulky trialkylphosphine accomplishes a broad spectrum of coupling processes, including Suzuki, Stille, Negishi, and Heck reactions. These methods have been applied in a wide array of settings, such as natural-product synthesis, materials science, and bioorganic chemistry.", "date": "2008-11-18", "date_type": "published", "publication": "Accounts of Chemical Research", "volume": "41", "number": "11", "publisher": "American Chemical Society", "pagerange": "1555-1564", "id_number": "CaltechAUTHORS:20200626-123754582", "issn": "0001-4842", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20200626-123754582", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH", "grant_number": "R01-GM62871" }, { "agency": "Merck Research Laboratories" }, { "agency": "Novartis" } ] }, "doi": "10.1021/ar800148f", "pmcid": "PMC2645957", "primary_object": { "basename": "nihms-86549.pdf", "url": "https://authors.library.caltech.edu/records/najr5-qdn45/files/nihms-86549.pdf" }, "resource_type": "article", "pub_year": "2008", "author_list": "Fu, Gregory C." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/xxfhs-0t411", "eprint_id": 85320, "eprint_status": "archive", "datestamp": "2023-08-20 06:30:19", "lastmod": "2023-10-18 18:05:53", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817" }, { "id": "Miller-S-J", "name": { "family": "Miller", "given": "Scott J." } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" } ] }, "title": "Ring-Closing Metathesis and Related Processes in Organic Synthesis", "ispublished": "pub", "full_text_status": "restricted", "note": "\u00a9 1995 American Chemical Society.\n\nReceived May 22, 1995.\n\nThis research was generously supported by the National\nInstitutes of Health. S.J.M. and G.C.F. are grateful to the\nNSF for postdoctoral fellowships.", "abstract": "Carbon-carbon bond forming reactions remain among the most important for the synthesis of organic structures. The transition metal alkylidene-catalyzed olefin metathesis reaction (eq 1) and the related transition metal alkylidene-mediated carbonyl olefination reaction (eq 2) are two such processes. Historically, olefin metathesis has been studied extensively both from the mechanistic standpoint and in the context of polymer synthesis. In contrast, its application to the synthesis of complex organic molecules and natural products has been limited. The related reaction, transition metal-mediated carbonyl olefination, is not as extensively studied mechanistically nor in synthetic applications. Among the reasons for this\ngap in methodology has been the incompatibility of traditional catalysts with the polar functional groups\ntypically encountered in organic synthesis.", "date": "1995-11-01", "date_type": "published", "publication": "Accounts of Chemical Research", "volume": "28", "number": "11", "publisher": "American Chemical Society", "pagerange": "446-452", "id_number": "CaltechAUTHORS:20180315-071849342", "issn": "0001-4842", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180315-071849342", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH" }, { "agency": "NSF Postdoctoral Fellowship" } ] }, "doi": "10.1021/ar00059a002", "resource_type": "article", "pub_year": "1995", "author_list": "Grubbs, Robert H.; Miller, Scott J.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/2xqxj-4j258", "eprint_id": 86724, "eprint_status": "archive", "datestamp": "2023-08-20 04:32:06", "lastmod": "2023-10-18 19:56:06", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Fujimura-Osamu", "name": { "family": "Fujimura", "given": "Osamu" } }, { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" }, { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817" } ] }, "title": "The Synthesis of Cyclic Enol Ethers via Molybdenum Alkylidene-Catalyzed Ring-Closing Metathesis", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 1994 American Chemical Society. \n\nReceived January 21, 1994 (Revised Manuscript Received May 23, 1994) \n\nSupport has been provided by the National Institutes of Health. Fellowship support for O.F. by the Ube Industries, Ltd., is gratefully acknowledged. O.F. thanks Dr. Z. Wu for helpful discussions.\n\nSupplemental Material - jo00094a002_si_001.pdf
", "abstract": "An efficient method for the construction of five- and six-membered cyclic vinyl ethers from unsaturated esters using stoichiometric titanium reagents to convert the esters to acyclic olefinic enol ethers which are then transformed to the desired products by catalytic ring-closing olefin metathesis with a molybdenum alkylidene complex is described.", "date": "1994-07-29", "date_type": "published", "publication": "Journal of Organic Chemistry", "volume": "59", "number": "15", "publisher": "American Chemical Society", "pagerange": "4029-4031", "id_number": "CaltechAUTHORS:20180530-141851654", "issn": "0022-3263", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180530-141851654", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NIH" }, { "agency": "Ube Industries, Ltd." } ] }, "other_numbering_system": { "items": [ { "id": "8961", "name": "Arnold and Mabel Beckman Laboratories of Chemical Synthesis" } ] }, "doi": "10.1021/jo00094a002", "primary_object": { "basename": "jo00094a002_si_001.pdf", "url": "https://authors.library.caltech.edu/records/2xqxj-4j258/files/jo00094a002_si_001.pdf" }, "resource_type": "article", "pub_year": "1994", "author_list": "Fujimura, Osamu; Fu, Gregory C.; et el." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/f6qpf-26e94", "eprint_id": 86400, "eprint_status": "archive", "datestamp": "2023-08-20 02:42:11", "lastmod": "2023-10-18 19:33:24", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" }, { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817" } ] }, "title": "Synthesis of cycloalkenes via alkylidene-mediated olefin metathesis and carbonyl olefination", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 1993 American Chemical Society. \n\nReceived January 6, 1993. \n\nSupport has been provided by the National Science Foundation (postdoctoral fellowship to G.C.F.) and the National Institutes of Health. We thank David Mai for technical assistance.\n\nSupplemental Material - ja00062a066_si_001.pdf
Supplemental Material - ja3800.pdf
", "abstract": "The development of efficient methods for constructing carbocycles continues to be an important goal of synthetic organic chemistry. One extremely useful approach to the formation of unsaturated carbocycles is the intramolecular dicarbonyl coupling reaction (eq 1). Oftentimes, the substrate employed in this process is generated by oxidation of a diene or of an olefinic ketone. In this communication, we report that transition-metal alkylidenes effect the direct synthesis of unsaturated carbocycles from either of these precursors (eqs 2 and 3).", "date": "1993-05-05", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "115", "number": "9", "publisher": "American Chemical Society", "pagerange": "3800-3801", "id_number": "CaltechAUTHORS:20180514-160629402", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180514-160629402", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF Postdoctoral Fellowship" }, { "agency": "NIH" } ] }, "other_numbering_system": { "items": [ { "id": "8781", "name": "Caltech Arnold and Mabel Laboratories of Chemical Synthesis" } ] }, "doi": "10.1021/ja00062a066", "primary_object": { "basename": "ja00062a066_si_001.pdf", "url": "https://authors.library.caltech.edu/records/f6qpf-26e94/files/ja00062a066_si_001.pdf" }, "related_objects": [ { "basename": "ja3800.pdf", "url": "https://authors.library.caltech.edu/records/f6qpf-26e94/files/ja3800.pdf" } ], "resource_type": "article", "pub_year": "1993", "author_list": "Fu, Gregory C. and Grubbs, Robert H." }, { "id": "https://authors.library.caltech.eduhttps://authors.library.caltech.edu/records/b32ce-kvg42", "eprint_id": 88219, "eprint_status": "archive", "datestamp": "2023-08-20 01:26:10", "lastmod": "2023-10-18 21:53:28", "type": "article", "metadata_visibility": "show", "creators": { "items": [ { "id": "Fu-G-C", "name": { "family": "Fu", "given": "Gregory C." }, "orcid": "0000-0002-0927-680X" }, { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817" } ] }, "title": "The application of catalytic ring-closing olefin metathesis to the synthesis of unsaturated oxygen heterocycles", "ispublished": "pub", "full_text_status": "public", "note": "\u00a9 1992 American Chemical Society. \n\nReceived February 13, 1992. \n\nSupport has been provided by the National Science Foundation (grant to R.H.G. and postdoctoral fellowship to G.C.F.) and the National Institutes of Health.\n\nSupplemental Material - ja00039a065_si_001.pdf
", "abstract": "The development of general approaches to carbon-carbon bond formation represents an important ongoing challenge for synthetic organic chemists. One efficient method for constructing carbon-carbon double bonds, the transition metal alkylidene-catalyzed olefin metathesis reaction (eq 1), has been the focus of intense interest in recent years from the standpoint of both mechanism and polymer synthesis; in contrast, use of this transformation in organic synthesis has been limited. As part of a broader program directed toward establishing transition metal alkylidenes as versatile reagents for organic chemistry, we report the successful application of catalytic olefin metathesis to the generation of a variety of unsaturated oxygen heterocycles.", "date": "1992-06-17", "date_type": "published", "publication": "Journal of the American Chemical Society", "volume": "114", "number": "13", "publisher": "American Chemical Society", "pagerange": "5426-5427", "id_number": "CaltechAUTHORS:20180724-152025829", "issn": "0002-7863", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180724-152025829", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF Postdoctoral Fellowship" }, { "agency": "NIH" } ] }, "other_numbering_system": { "items": [ { "id": "8575", "name": "Arnold and Mabel Beckman Laboratories of Chemical Synthesis" } ] }, "doi": "10.1021/ja00039a065", "primary_object": { "basename": "ja00039a065_si_001.pdf", "url": "https://authors.library.caltech.edu/records/b32ce-kvg42/files/ja00039a065_si_001.pdf" }, "resource_type": "article", "pub_year": "1992", "author_list": "Fu, Gregory C. and Grubbs, Robert H." } ]