Bifunctional Aziridines from Photochemically Generated FSO ₂ NH ₂ for SuFEx Diversification of Alkenes

Sulfonyl fluorides have emerged as ubiquitous reactive motifs in fields ranging from medicinal chemistry to materials science, with applications as chemical warheads and as clickable units via Sulfur(VI) Fluoride Exchange (SuFEx). However, methods for introducing sulfamoyl fluorides, the nitrogen-containing congeners, into functional-group rich scaffolds remain scarce. Herein, we report the synthesis of fluorosulfonyl aziridines from FSO₂NH₂ as a versatile and modular platform for alkene diversification. A safe and practical synthesis of FSO₂NH₂ was optimized via photodegradation of fluorosulfonyl azide (FSO₂N₃) in solution, enabling the development of a Rh-catalyzed aziridination with a broad alkene scope that merges the innate reactivity of the strained heterocycle with the modularity of SuFEx click chemistry. The unprecedented bifunctional electrophile was exploited in selective reactions with a wide array of nucleophiles under mild conditions, delivering sulfamoyl fluorides as well as S(VI)-containing linkages of pharmaceutical relevance, including sulfamides and sulfamate esters.