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

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja4054114DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja4054114PublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3803154/PubMed CentralArticle
ORCID:
AuthorORCID
Fu, Gregory C.0000-0002-0927-680X
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.
Funders:
Funding AgencyGrant Number
NIHR01-GM62871
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: Jason Perez
Deposited On:24 Oct 2013 21:55
Last Modified:10 Nov 2021 04:37

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