Copper‐Catalyzed Enantioselective Decarboxylative Cyanation of Carboxylic Acids via Electrophotocatalysis

Carboxylic acids are important chemical feedstocks, and direct decarboxylative asymmetric transformation holds significant synthetic value. Herein, we report a copper‐catalyzed direct enantioselective decarboxylative cyanation of benzyl carboxylic acids under electrophotocatalytic conditions. Benzylic radicals are efficiently generated via ligand–to–metal charge transfer of copper(II) carboxylate species under irradiation of blue LEDs. Concurrently, the generation of copper(II) cyanide occurred simultaneously at the anode via electro‐oxidation, avoiding the use of the stoichiometric amount of chemical oxidants. Then the coupling of benzylic radical and chiral Cu(II) cyanide leads to enantioselective decarboxylative cyanation. This reaction features a broad substrate scope and excellent functional group tolerance, enabling the direct conversion of carboxylic acids into diverse chiral benzyl nitriles.