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Rhodium‐Catalyzed Stereoselective Amination of Thioethers with N‐Mesyloxycarbamates: DMAP and Bis(DMAP)CH2Cl2 as Key Additives |
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| Authors: | Prof Dr Hélène Lebel Henri Piras Johan Bartholoméüs |
| Institution: | 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. |
| Keywords: | asymmetric catalysis chiral sulfilimines metal nitrenes rhodium sulfoximines |