Cordier, Christopher J. and Lundgren, Ryan J. and Fu, Gregory C. (2013) Enantioconvergent Cross-Couplings of Racemic Alkylmetal Reagents with Unactivated Secondary Alkyl Electrophiles: Catalytic Asymmetric Negishi α-Alkylations of N-Boc-pyrrolidine. Journal of the American Chemical Society, 135 (30). pp. 10946-10949. ISSN 0002-7863. PMCID PMC3803154. doi:10.1021/ja4054114. https://resolver.caltech.edu/CaltechAUTHORS:20131024-101621144
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Abstract
Although enantioconvergent alkyl–alkyl 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 α-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 β-hydride elimination/β-migratory insertion pathway) are unlikely to be operative.
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Additional Information: | © 2013 American Chemical Society. Received: May 30, 2013; Published: July 19, 2013. We 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. | ||||||||||||
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Issue or Number: | 30 | ||||||||||||
PubMed Central ID: | PMC3803154 | ||||||||||||
DOI: | 10.1021/ja4054114 | ||||||||||||
Record Number: | CaltechAUTHORS:20131024-101621144 | ||||||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20131024-101621144 | ||||||||||||
Official Citation: | Enantioconvergent Cross-Couplings of Racemic Alkylmetal Reagents with Unactivated Secondary Alkyl Electrophiles: Catalytic Asymmetric Negishi α-Alkylations of N-Boc-pyrrolidine Christopher J. Cordier, Rylan J. Lundgren, and Gregory C. Fu Journal of the American Chemical Society 2013 135 (30), 10946-10949 | ||||||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||||||
ID Code: | 42041 | ||||||||||||
Collection: | CaltechAUTHORS | ||||||||||||
Deposited By: | INVALID USER | ||||||||||||
Deposited On: | 24 Oct 2013 21:55 | ||||||||||||
Last Modified: | 10 Nov 2021 04:37 |
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