Photoredox Catalysis for the Synthesis of N‐CF2H Compounds Using 1‐((N‐(difluoromethyl)‐4‐methylphenyl)‐sulfonamido)pyridin‐1‐ium Trifluoromethanesulfonate

Abstract N ‐(difluoromethyl)amino (−NCF 2 H) compounds are of great interest given their unique and underexplored physiochemical properties. The lack of structural diversity in NCF 2 H compounds is likely due in part to the shortage of protocols for efficient installation. Presented herein is a new shelf‐stable pyridinium reagent that enables the direct installation of the N ‐(difluoromethyl)sulfonamide moiety [N(Ts)CF 2 H)] onto (hetero)arenes and alkenes for the diversification of aryl and alkyl NCF 2 H compounds. The described protocol utilizes blue light photoredox catalysis and displays broad functional group tolerance with excellent chemoselectivity. Additional transformations and applicability towards a photoredox continuous flow protocol are also demonstrated.