Mechanochemical syntheses of N-acyl sulfinamidines via iron-nitrenoids and their conversions to sulfur(VI) derivatives

Herein, we present an iron-catalyzed mechanochemical synthesis of N -acyl sulfinamidines via nitrenoids generated from dioxazolones. Various substituents on both sulfenamides and thiols are well tolerated, giving a broad range of products in good to excellent yields under solvent-free ambient conditions. Potential synthetic applications of the resulting sulfinamidines are demonstrated by diverse transformations, such as fluorination, sulfur–fluoride exchange, oxidation, and deprotection. A variety of aza-sulfur(VI) derivatives, including sulfondiimidoyl fluorides, sulfondiimines, sulfondiimidoyl esters, and sulfonimidamides were successfully synthesized. Starting from either sulfenamides or thiols, mechanochemical syntheses via iron-nitrenoids lead to N -acyl sulfinamidines in good to excellent yields. By subsequent fluorinations, sulfur–fluoride exchange reactions, oxidations, and deprotection procedures, the products can be converted into a range of aza-sulfur(VI) derivatives.