Direct Fluorosulfonamidation of (Hetero)arenes and Alkenes with Photoredox-Active Fluorosulfamoyl Radical Reagents
Ting Xiong, Qilong Chen, Ziyan Zhang, Gui Lu, Jiang Weng
Abstract
Sulfur(VI) fluoride exchange (SuFEx) is a second-generation click chemistry reaction that relies on the unique reactivities of S VI –F bonds. The development of efficient methods for incorporating a S(VI)–F motif into molecules is of great significance. Sulfamoyl fluorides (R 1 R 2 NSO 2 F), serving as versatile SuFExable hubs, are typically synthesized by using “ + SO 2 F” reagents to establish N-SO 2 F 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 (•NSO 2 F) precursors, the direct installation of the NSO 2 F 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 (R 1 R 2 NSO 2 F) under mild photocatalytic conditions and has been applied in the late-stage functionalization of pharmaceuticals and peptides.