Journal
ORGANOMETALLICS
Volume 40, Issue 19, Pages 3267-3275Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.organomet.1c00367
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Funding
- Natural Sciences and Engineering Research Council of Canada (NSERC) (Canada)
- Canadian Foundation for Innovation
- Canada Research Chair Program
- Universite de Montreal
- Ministry of Higher Education and Scientific Research of Tunisia
- Canada Foundation for Innovation (CFI)
- Ministere de l'Economie, des Sciences et de l'Innovation du Quebec (MESI)
- Fonds de recherche du QuebecNature et technologies (FRQ-NT)
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The rhodium-catalyzed sulfimidation reaction involves key intermediates of rhodium nitrene and rhodium nitrenoid species, with DMAP and bis-(DMAP)CH2Cl2 additives playing crucial roles in stabilizing these intermediates. The addition of different ligands can diverge the reaction mechanism, as demonstrated by experimental and theoretical studies, showing that the involvement of DMAP ligand is essential for the stabilization of intermediates.
The rhodium-catalyzed sulfimidation of thioethers using N-mesyloxycarbamates is a powerful tool to access chiral sulfilimines. 4-Dimethylaminopyridine (DMAP) and bis-(DMAP)-CH2Cl2 additives were found to be crucial to achieving high yields and selectivities. Experimental studies have suggested that the reaction mechanism would involve a rhodium/nitrenoid complex rather than a rhodium/nitrene species. A density functional theory (DFT) study to investigate rhodium-catalyzed sulfimidation reactions is reported herein. Both rhodium nitrene and rhodium nitrenoid species were proposed as key intermediates for the amination reaction. The role of additives was investigated, showing that the apical DMAP ligand was crucial to stabilize the rhodium nitrene intermediate. Furthermore, adding bis-(DMAP)CH2Cl2 diverges the reaction mechanism from a rhodium nitrene insertion to a substitution-like reaction of the rhodium nitrenoid complex. This deviation was demonstrated to be substrate-dependent, which is in agreement with the experimental Hammett study.
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