Cobaloxime Catalysis for Enamine Phosphorylation with Hydrogen Evolution

Direct phosphorylation of enamine and enamide with hydrogen evolution was realized via cobaloxime catalysis under visible-light irradiation. Control experiments and spectro- R scopic studies demonstrated a reductive quenching pathway of cobaloxime catalyst to produce phosphinoyl radical, which underwent cross-coupling with various enamines and enamides) to give diverse beta-phosphinoyl products in good to excellent yields. More interestingly, Z/E mixture of acyclic enamines could convert into single Z-products with good reactivity.