Rhodium-Catalyzed Stereoselective Amination of Thioethers with N-Mesyloxycarbamates: DMAP and Bis(DMAP)CH 2Cl2 as Key Additives. -Chiral sulfilimines are prepared by rhodium-catalyzed intermolecular amination of thioethers with the readily available N-mesyloxycarbamate (I). DMAP and the related dimer BDC turn out to be crucial catalytic additives for improved diastereoselectivity. Cyclic voltametric measurements suggest a Rh(II)-Rh(III) complex as the catalytically active species. -(LEBEL*, H.; PIRAS, H.; BARTHOLOMEUES, J.; Angew. Chem., Int. Ed. 53 (2014) 28, 7300-7304, http://dx.
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