Electrochemical α‐Acyloxylation by Cooperative Chiral Amine and Proton Shuttle Catalysis via an Asymmetric S N 1 Mechanism

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.