Publication details for Prof. AnnMarie C. O'DonoghueCollett, C. J., Massey, R. S., Taylor, J. E., Maguire, O. R., O'Donoghue, A. C. & Smith, A. D. (2015). Rate and Equilibrium Constants for the Addition of N-Heterocyclic Carbenes into Benzaldehydes: A Remarkable 2-Substituent Effect. Angewandte Chemie International Edition 54(23): 6887-6892.
- Publication type: Journal Article
- ISSN/ISBN: 1433-7851, 1521-3773
- DOI: 10.1002/anie.201501840
- Keywords: 2-substituent effect, Kinetics, Mechanistic studies, N-heterocyclic carbenes, Organocatalysis.
- Further publication details on publisher web site
- Durham Research Online (DRO) - may include full text
Author(s) from Durham
Rate and equilibrium constants for the reaction between N-aryl triazolium N-heterocyclic carbene (NHC) precatalysts and substituted benzaldehyde derivatives to form 3-(hydroxybenzyl)azolium adducts under both catalytic and stoichiometric conditions have been measured. Kinetic analysis and reaction profile fitting of both the forward and reverse reactions, plus onwards reaction to the Breslow intermediate, demonstrate the remarkable effect of the benzaldehyde 2-substituent in these reactions and provide insight into the chemoselectivity of cross-benzoin reactions.