Département de Chimie, Center for Green Chemistry and Catalysis, Université de Montréal, C.P. 6128, Succ. Centre‐ville, Montréal, Québec, H3C 3J7 Canada
Abstract:
A stereoselective Rh‐catalyzed intermolecular amination of thioethers using a readily available chiral N‐mesyloxycarbamate to produce sulfilimines in excellent yields and diastereomeric ratio is described. A catalytic mixture of 4‐dimethylaminopyridine (DMAP) and bis(DMAP)CH2Cl2 proved pivotal in achieving high selectivity. The X‐ray crystal structure of the (DMAP)2?Rh2{(S)‐nttl}4] complex was obtained and mechanistic studies suggested a RhII‐RhIII complex as the catalytically active species.