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.