Direct Fluorosulfonamidation of (Hetero)arenes and Alkenes with Photoredox-Active Fluorosulfamoyl Radical Reagents

Sulfur(VI) fluoride exchange (SuFEx) is a second-generation click chemistry reaction that relies on the unique reactivities of SVI–F bonds. The development of efficient methods for incorporating a S(VI)–F motif into molecules is of great significance. Sulfamoyl fluorides (R1R2NSO2F), serving as versatile SuFExable hubs, are typically synthesized by using “+SO2F” reagents to establish N-SO2F bonds. In this study, we report the development of N-fluorosulfamoyl pyridium salts (NFSAPs) as radical fluorosulfonamidation reagents that are readily accessible and bench-stable. By employing NFSAPs as essential fluorosulfamoyl radical (•NSO2F) precursors, the direct installation of the NSO2F group onto (hetero)arenes and alkenes is achieved through distinct C–N bond formation reactions. This platform facilitates the collective synthesis of highly functionalized N-aryl, N-alkyl, and N-alkenyl sulfamoyl fluorides (R1R2NSO2F) under mild photocatalytic conditions and has been applied in the late-stage functionalization of pharmaceuticals and peptides.