4.8 Article

Mechanism of the Rhodium(III)-Catalyzed Arylation of Imines via C-H Bond Functionalization: Inhibition by Substrate

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 134, Issue 3, Pages 1482-1485

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/ja211110h

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Funding

  1. NIH [GM069559]
  2. Office of Energy Research, Office of Basic Energy Sciences, Chemical Sciences Division, U.S. DOE [DE-AC02-05CH11231]
  3. Deutsche Forschungsgemeinschaft [Ta 733/1-1, Ta 733/1-2]

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Rh(III)-catalyzed arylation of imines provides a new method for C C bond formation while simultaneously introducing an alpha-branched amine as a functional group. This detailed mechanistic study provides insights for the rational future development of this new reaction. Relevant intermediate Rh(III) complexes have been isolated and characterized, and their reactivities in stoichiometric reactions with relevant substrates have been monitored. The reaction was found to be first order in the catalyst resting state and inverse first order in the C-H activation substrate.

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