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Rhodium(II)-catalyzed C–H aminations using N-mesyloxycarbamates: reaction pathway and by-product formation

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Abstract

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 Rh–nitrene 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.

Graphical abstract: Rhodium(ii)-catalyzed C–H aminations using N-mesyloxycarbamates: reaction pathway and by-product formation

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Publication details

The article was received on 16 Jul 2018, accepted on 19 Oct 2018 and first published on 22 Oct 2018


Article type: Edge Article
DOI: 10.1039/C8SC03153C
Citation: Chem. Sci., 2019, Advance Article
  • Open access: Creative Commons BY license
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    Rhodium(II)-catalyzed C–H aminations using N-mesyloxycarbamates: reaction pathway and by-product formation

    E. Azek, M. Khalifa, J. Bartholoméüs, M. Ernzerhof and H. Lebel, Chem. Sci., 2019, Advance Article , DOI: 10.1039/C8SC03153C

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