ABSTRACT Electrochemical asymmetric radical reactions stand at the frontier of sustainable organic synthesis, yet precise enantiocontrol over short‐lived radical intermediates under electrochemical conditions remains a formidable challenge. Herein, we report a synergistic integration of electrocatalysis and asymmetric Lewis base catalysis that enables highly enantioselective radical functionalization of alkenes. This strategy centers on the anodic single‐electron oxidation of catalytically generated C1‐ammonium enolates—derived from simple esters and chiral isothiourea organocatalysts—to furnish chiral catalyst‐bound α‐acyl ammonium radical intermediates. Confined within the chiral cavity of the Lewis base catalyst, these tethered radicals undergo enantioselective addition to alkenes, and the resulting adduct radical is strategically diverted toward either difunctionalized or alkenylated products with high enantiocontrol (up to 99% ee). This work establishes a versatile platform that merges Lewis base catalysis with electrosynthesis for enantioselective alkene difunctionalization via direct ester C(sp 3 )─H activation, thereby fundamentally extending the scope of asymmetric Lewis base organocatalysis into the realm of electrocatalytic radical transformations.
Li et al. (Fri,) studied this question.