Sulfinylnitrenes via Chemoselective S–N Bond Cleavage: Design, Synthesis, and Applications

Herein, we report the development of bench-stable, scalable sulfinylnitrene precursors that enable the generation of reactive sulfinylnitrene intermediates via chemoselective S–N bond cleavage under thermal or photolytic conditions, without additives or pyrophoric reagents. These intermediates react with nucleophiles (N or O) to afford sulfonimidamides, a privileged pharmacophore, or sulfonimidates, a versatile intermediate in deoxygenating reactions. This operationally simple transformation provides a general strategy for S–N bond formation and enables late-stage functionalization of amines.