Nickel-Electrocatalyzed Anodic Enantioselective Acyloxylation and Cathodic Deacyloxylation of C–O Bonds

Abstract Asymmetric catalysis is indispensable for the synthesis of chiral molecules, yet it is typically constrained by thermodynamic and kinetic barriers. Achieving stereoselective bond formation and cleavage within a single, catalytic platform would dramatically expand the power and versatility of asymmetric catalysis. We present an enantioselective nickel-electrocatalytic system that utilizes a spin–center shift (SCS) mechanism to enable selective C–O linkage transformations. A variety of commercially available carboxylic acids and 2-acylimidazoles can be directly coupled through anodic oxidative cross-dehydrogenative acyloxylation with excellent enantiomeric excess (up to 99% ee), and the resulting esters can be cleaved to release the carboxylic acids and 2-acylimidazoles via cathodic reduction (up to 92% yield). Mechanistic exploration revealed that the ferrocene mediator promotes the oxidative coupling process while suppressing the reductive cleavage pathway. This asymmetric electrocatalytic strategy enables flexible C–O transformations, facilitating a highly stereoselective and efficient acyloxylation–deacyloxylation process.