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Enantioselective S_N1-type reaction via electrochemically generated chiral α-Imino carbocation intermediate.

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_N1 step proceeds via a tertiary amine-mediated proton shuttle that facilitates facial selection in reacting with carbocation.

SUBMITTER: Lin Q

PROVIDER: S-EPMC11319787 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature

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Enantioselective SN1-type reaction via electrochemically generated chiral α-Imino carbocation intermediate.

Lin Qifeng Q Duan Yingdong Y Li Yao Y Jian Ruijun R Yang Kai K Jia Zongbin Z Xia Yu Y Zhang Long L Luo Sanzhong S

Nature communications 20240812 1

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 ...[more]

PMID: 39134515

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