Radical Thiocyano(Selenocyano)trifluoromethylations of Alkenes on Water

Abstract Trifluoromethylation‐based difunctionalization of alkenes provides a step‐economical route to CF 3 ‐containing polyfunctionalized organics. New and scalable processes are highly desired in this field. Here, we report a simple and environmentally benign method for olefinic thiocyanotrifluoromethylation. Using PhICF 3 Cl as unique CF 3 agent and NaSCN as the SCN source, the difunctionalization of alkenes selectively occurs on water at ambient condition. Mechanism studies suggest a radical process in which SCN anion is proposed to act as not only reductive initiator but also S ‐nucleophile. All tested reactions are compatible with mono‐, di‐, tri‐, and tetra‐substituted alkenes and with high functional group tolerance. This method is also suitable for the selenocyanotrifluoromethylation of alkenes. Therefore, a sustainable platform has been established to synthesize valuable β ‐trifluoromethylated thio(seleno)cyanates in a green way.