Journal
CHEMICAL SCIENCE
Volume 10, Issue 3, Pages 718-729Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c8sc03153c
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Funding
- 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)
- le Ministere de l'Economie, des Sciences et de l'Innovation du Quebec (MESI)
- le Fonds de recherche du Quebec Nature et technologies (FRQ-NT)
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N-Mesyloxycarbamates are practical nitrene precursors that undergo C-H amination reactions in the presence of rhodium dimer catalysts. Under these conditions, both oxazolidinones and chiral amines have been prepared in a highly efficient manner. Given the elevated reactivity of the intermediates involved in the catalytic cycle, mechanistic details have remained hypothetical, relying on indirect experiments. Herein a density functional theory (DFT) study is presented to validate the catalytic cycle of the rhodium-catalyzed C-H amination with N-mesyloxycarbamates. A concerted pathway involving Rhnitrene species that undergoes C-H insertion is found to be favored over a stepwise C-N bond formation manifold. Density functional calculations and kinetic studies suggest that the rate-limiting step is the C-H insertion process rather than the formation of Rh-nitrene species. In addition, these studies provide mechanistic details about competitive by-product formation, resulting from an intermolecular reaction between the Rh-nitrene species and the N-mesyloxycarbamate anion.
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