Mechanochemical Conditions for Intramolecular N−O Couplings via Rhodium Nitrenoids Generated from <i>N</i>‐Acyl Sulfonimidamides
Shulei Pan, Peng Wu, Dimitra Bampi, Jas S. Ward, Kari Rissanen, Carsten Bolm
Abstract
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.
Topics & Concepts
RhodiumIntramolecular forceNitreneChemistryCatalysisSulfoxideSolventInertPhotochemistryMedicinal chemistryPolymer chemistryOrganic chemistrySynthesis and Catalytic ReactionsCatalytic C–H Functionalization MethodsPhenothiazines and Benzothiazines Synthesis and Activities