Issue 1, 2012

The effect of the N-mesityl group in NHC-catalyzed reactions

Abstract

The majority of N-heterocyclic carbene catalyzed reactions of α-functionalized aldehydes, including annulations, oxidations, and redox reactions, occur more rapidly with N-mesityl substituted NHCs. In many cases, no reaction occurs with NHCs lacking ortho-substituted aromatics. By careful competition studies, catalyst analogue synthesis, mechanistic investigations, and consideration of the elementary steps in NHC-catalyzed reactions of enals, we have determined that the effect of the N-mesityl group is to render the initial addition of the NHC to the aldehyde irreversible, thereby accelerating the formation of the Breslow intermediate. These studies rationalize the experimentally observed catalyst preference for all classes of NHC-catalyzed reactions of aldehydes and provide a roadmap for catalyst selection and design.

Graphical abstract: The effect of the N-mesityl group in NHC-catalyzed reactions

Supplementary files

Article information

Article type
Edge Article
Submitted
26 Jun 2011
Accepted
18 Jul 2011
First published
18 Aug 2011

Chem. Sci., 2012,3, 192-197

The effect of the N-mesityl group in NHC-catalyzed reactions

J. Mahatthananchai and J. W. Bode, Chem. Sci., 2012, 3, 192 DOI: 10.1039/C1SC00397F

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