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Enantioconvergent Cross−Couplings of Alkyl Electrophiles: The Catalytic Asymmetric Synthesis of Organosilanes

Fu, Gregory C. (2019) Enantioconvergent Cross−Couplings of Alkyl Electrophiles: The Catalytic Asymmetric Synthesis of Organosilanes. Angewandte Chemie International Edition, 58 (11). pp. 3571-3574. ISSN 1433-7851. http://resolver.caltech.edu/CaltechAUTHORS:20190122-084528318

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Abstract

Metal‐catalyzed enantioconvergent cross‐coupling 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/π orbital. Herein, we demonstrate for the first time that enantioconvergent cross‐couplings can be achieved with electrophiles that lack such features; specifically, we establish that a chiral nickel catalyst can accomplish Negishi reactions of racemic α‐halosilanes with alkylzinc reagents with good enantioselectivity under simple and mild conditions, thereby providing access to enantioenriched organosilanes, an important class of target molecules.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1002/anie.201814208DOIArticle
ORCID:
AuthorORCID
Fu, Gregory C.0000-0002-0927-680X
Additional Information:© 2019 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim. Manuscript received: December 13, 2018; Accepted manuscript online: January 16, 2019; Version of record online: February 5, 2019. Support has been provided by the National Institutes of Health (National Institute of General Medical Sciences; grant R01–GM062871 to G.C.F. and grant F32–GM116234 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. The authors declare no conflict of interest.
Funders:
Funding AgencyGrant Number
NIHR01 GM062871
NIH Postdoctoral FellowshipF32 GM116234
Dow Next Generation Educator FundUNSPECIFIED
Subject Keywords:alkylation; asymmetric catalysis; cross-coupling; nickel; silicon
Record Number:CaltechAUTHORS:20190122-084528318
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20190122-084528318
Official Citation:G. M. Schwarzwalder, C. D. Matier, G. C. Fu, Angew. Chem. Int. Ed. 2019, 58, 3571; doi: 10.1002/anie.201814208
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:92389
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:22 Jan 2019 20:15
Last Modified:06 Mar 2019 16:14

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