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Rhodium‐Catalyzed Stereoselective Amination of Thioethers with N ‐Mesyloxycarbamates: DMAP and Bis(DMAP)CH 2 Cl 2 as Key Additives
Author(s) -
Lebel Hélène,
Piras Henri,
Bartholoméüs Johan
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201402961
Subject(s) - chemistry , amination , stereoselectivity , diastereomer , rhodium , catalysis , selectivity , medicinal chemistry , intermolecular force , organic chemistry , molecule
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)CH 2 Cl 2 proved pivotal in achieving high selectivity. The X‐ray crystal structure of the (DMAP) 2 ⋅[Rh 2 {( S )‐nttl} 4 ] complex was obtained and mechanistic studies suggested a Rh II ‐Rh III complex as the catalytically active species.