Electrochemical α‐Acyloxylation by Cooperative Chiral Amine and Proton Shuttle Catalysis via an Asymmetric S N 1 Mechanism
Na Zhang, Wenzhuo Xu, Jiawei Li, Pengxin Zhou, Qifeng Lin, Sanzhong LuoABSTRACT
Asymmetric S N 1 reactions offer a powerful approach to enantioenriched molecules but remain challenging in carbocation generation and proton manipulation. Herein, we report an electrochemical asymmetric α‐acyloxylation of aldehydes through an α‐imino carbocation intermediate generated by aminocatalysis and anodic oxidation. A catalytic imidazole derivative serves as a recyclable proton shuttle, facilitating cathodic hydrogen evolution. The reaction scope was systematically evaluated using a ScopeMap‐guided substrate‐selection strategy, enabling uniform sampling of the chemical space. Mechanistic studies support the crucial role of the proton shuttle in facilitating chemical transformation and the catalytic cycle.