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Published July 31, 2013 | Supplemental Material + Accepted Version
Journal Article Open

Enantioconvergent Cross-Couplings of Racemic Alkylmetal Reagents with Unactivated Secondary Alkyl Electrophiles: Catalytic Asymmetric Negishi α-Alkylations of N-Boc-pyrrolidine

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.

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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Accepted Version - nihms508343.pdf

Supplemental Material - ja4054114_si_001.pdf

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August 19, 2023
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