Selectivity Control in Visible-Light-Induced Three-Component Cascade Thiolation–Difluoroalkylation of Alkynes

A visible-light-induced three-component regioselective thiolation-difluoroalkylation of alkynes is reported. This mild reaction system is compatible with a wide range of unactivated alkynes, trifluoromethylarenes, and thiols, enabling the selective formation of gem-difluoroalkyl thioethers with acetylene substituents distal to the sulfur atom. This regioselectivity is achieved through an accurate reaction cascade of sequential thiolation and difluoroalkylation.