Pyridinium-Based Fluorosulfonamide Reagents Enabled Photoredox-Catalyzed Radical Fluorosulfonamidation.

Sulfamoyl fluorides, as a crucial building block of SuFEx, have garnered extensive research interest due to their unique properties. However, the direct radical fluorosulfonamidation process for the synthesis of sulfamoyl fluorides has been overlooked. We herein disclosed a practical procedure for constructing a redox-active fluorosulfonamide radical reagent named fluorosulfonyl- N -pyridinium tetrafluoroborate (PNSF) from SO 2 F 2 . These reagents can facilitate a range of reactions, including the N -(fluorosulfonyl) sulfonamidation of (hetero)arenes, sequential radical stereoselective fluorosulfonamidation, and 1,2-difunctionalization of alkenes.