Enantioselective S<sub>N</sub>1-type reaction via electrochemically generated chiral α-Imino carbocation intermediate.

Lin, Qifeng; Duan, Yingdong; Li, Yao; Jian, Ruijun; Yang, Kai; Jia, Zongbin; Xia, Yu; Zhang, Long et al. · Nat Commun · 2024

basic_science · Level V

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Abstract

Electrochemical reactions via carbocation intermediates remain fundamental transformations that build up molecular functionality and complexity in a sustainable manner. Enantioselective control of such processes is a great challenge in a highly ionic electrolyte solution. Here, we report an anodic generation of chiral α-imino carbocation intermediates by enamine catalysis. The chiral carbocation intermediates can be intercepted by a variety of nucleophiles such as alcohols, water and thiols with high stereoselectivity. The key S<sub>N</sub>1 step proceeds via a tertiary amine-mediated proton shuttle that facilitates facial selection in reacting with carbocation.