Mechanochemical Conditions for Intramolecular N–O Couplings via Rhodium Nitrenoids Generated from N‐Acyl Sulfonimidamides

Starting from N‐acyl sulfonimidamides, mechanochemically generated rhodium nitrenoids undergo intramolecular N–O couplings to provide unprecedented 1,3,2,4‐oxathiadiazole 3‐oxides in good to excellent yields. The cyclization proceeds efficiently with a catalyst loading of only 0.5 mol% in the presence of phenyliodine(III) diacetate (PIDA) as oxidant. Neither an inert atmosphere nor additional heating is required in this solvent‐free procedure. Under heat or blue light, the newly formed five‐membered heterocycles function as nitrene precursors reacting with sulfoxides as exemplified by the imidation of dimethyl sulfoxide.