Electrochemical Conversions of Sulfenamides into Sulfonimidoyl- and Sulfondiimidoyl Fluorides

The invention of versatile linkage agents provides the chemical basis for SuFEx chemistry. Sulfonimidoyl fluorides and sulfondiimidoyl fluorides are aza-isosteres of sulfonyl fluorides with diverse reactivity through the fine-tuning of N-substituents. However, limited synthetic approaches impede their wide applications in SuFEx chemistry. Herein, we develop a straightforward electrochemical strategy for sulfonimidoyl- and sulfondiimidoyl fluorides through sequential oxidations of the readily available sulfenamides via sulfinamide and iminosulfinamide intermediates, respectively. The previously rarely investigated (bis)sulfondiimidoyl fluorides are now easily accessible and readily participate in SuFEx chemistry with diverse oxygen and nitrogen nucleophiles, macrocyclization, and polymerization.