Electrochemical C–H phosphorothiolation of indolizines with thiocyanate and phosphite in one pot

A facile and practical protocol for C–H phosphorothiolation of indolizines using thiocyanate as the sulfur source and phosphite as the phosphorylated reagent has been developed. A broad range of substrates were well tolerated and the desired products were obtained in moderate to excellent yields. Moreover, the reaction involved electrochemical thiocyanation of indolizines and a chemical process to construct the S–P bond in the presence of DBU. A plausible EC mechanism for this reaction has been revealed by cyclic voltammetry and control experiments. This method provided a green pathway to synthesize S-(hetero)aryl phosphorothioates by electrochemical oxidation at room temperature without external oxidants and transition metal catalysts.