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 <i>N</i>-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.