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J Am Chem Soc. 2006 Feb 22;128(7):2452-62.

Experimental and computational studies on the mechanism of N-heterocycle C-H activation by Rh(I).

Author information

1
Department of Chemistry, University of California, and Division of Chemical Sciences, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.

Abstract

Evidence is presented for a proposed mechanism of C-H activation of 3-methyl-3,4-dihydroquinazoline (1) by (PCy(3))(2)RhCl. One intermediate (3), a coordination complex of 1 with (PCy(3))(2)RhCl, was identified along the path to the Rh-N-heterocyclic carbene product of this reaction (2). Isotopic labeling and reaction-rate studies were used to demonstrate that C-H activation takes place intramolecularly on the reaction coordinate between 3 and 2. Computational studies corroborate the proposed mechanism and suggest that the rate-limiting step is oxidative addition of the C-H bond to the metal center. The consequences of this mechanism for coupling reactions of N-heterocycles that occur via Rh-catalyzed C-H bond activation are discussed.

PMID:
16478202
PMCID:
PMC2585050
DOI:
10.1021/ja0576684
[Indexed for MEDLINE]
Free PMC Article

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