Lewis Base-Electrocatalyzed Enantioselective Radical Cross-Coupling of Esters

The merger of electrochemistry and Lewis base catalysis represents a pioneering paradigm in asymmetric electrosynthesis, exploiting a sustainable and efficient strategy for the α-functionalization of simple esters. Herein, we report a highly enantioselective Lewis base-electrocatalyzed oxidative α-coupling of esters with allylsilanes, allenylsilanes, and potassium alkenyl trifluoroborates. The success of this transformation hinges on the synergistic combination of anodic electrolysis and Lewis base catalysis, which enables the facile conversion of C1-ammonium enolates into chiral isothiourea-bound α-carbonyl radical species. These intermediates, by virtue of their exceptional stereochemical control, pave the way for subsequent high-fidelity asymmetric radical transformations, providing access to allylated, dienylated, and alkenylated ester derivatives in high yields with excellent stereocontrol (up to 99% ee) under mild conditions. This Lewis base electrochemistry platform opens new avenues for stereochemical control in radical reactions and offers opportunities for broader applications in asymmetric synthesis.