title: The effect of theN-mesityl group in NHC-catalyzed reactions.
abstract: The majority of N-heterocyclic carbene catalyzed reactions ofα-functionalized aldehydes, including annulations, oxidations, and redox reactions, occur more rapidly withN-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 theN-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.
authors.forename: Jessada
authors.initials: J
authors.lastname: Mahatthananchai
authors.forename: Jeffrey W
authors.initials: JW
authors.lastname: Bode