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Catalytic Enantioconvergent Couplings of Secondary and Tertiary Electrophiles with Olefins

Wang, Zhaobin and Yin, Haolin and Fu, Gregory C. (2018) Catalytic Enantioconvergent Couplings of Secondary and Tertiary Electrophiles with Olefins. Nature, 563 (7731). pp. 379-383. ISSN 0028-0836. https://resolver.caltech.edu/CaltechAUTHORS:20181002-161720440

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Abstract

Carbon–carbon bonds, including those between sp^3-hybridized carbon atoms (alkyl–alkyl 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–alkyl bonds and control stereochemistry is important, although challenging. Here we describe a strategy for enantioselective alkyl–alkyl 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—including secondary and tertiary electrophiles, which have not previously been shown to be suitable for enantioconvergent coupling with alkyl metal nucleophiles—cross-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–alkyl coupling.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1038/s41586-018-0669-yDOIArticle
https://rdcu.be/9PCcPublisherFree ReadCube access
ORCID:
AuthorORCID
Fu, Gregory C.0000-0002-0927-680X
Additional Information:© 2018 Springer Nature Limited. Received 30 April 2018; Accepted 11 October 2018; Published 18 October 2018. Data 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 1822790–1822793, 1839344–1839346 and 1861568). Support 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 L. M. Henling, D. G. VanderVelde and S. C. Virgil for assistance and discussions. Author 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. The authors declare no competing interests.
Funders:
Funding AgencyGrant Number
NIHR01-GM62871
Gordon and Betty Moore FoundationUNSPECIFIED
Issue or Number:7731
Record Number:CaltechAUTHORS:20181002-161720440
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20181002-161720440
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:90086
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:22 Oct 2018 21:52
Last Modified:03 Oct 2019 20:22

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