Collett, C. J. and Massey, R. S. and Taylor, J. E. and Maguire, O. R. and O'Donoghue, A. C. and 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). pp. 6887-6892.
Abstract
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.
| Item Type: | Article |
|---|---|
| Keywords: | 2-substituent effect, Kinetics, Mechanistic studies, N-heterocyclic carbenes, Organocatalysis. |
| Full text: | (VoR) Version of Record Available under License - Creative Commons Attribution. Download PDF (698Kb) |
| Status: | Peer-reviewed |
| Publisher Web site: | http://dx.doi.org/10.1002/anie.201501840 |
| Publisher statement: | © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
| Date accepted: | No date available |
| Date deposited: | 28 October 2015 |
| Date of first online publication: | 23 April 2015 |
| Date first made open access: | 28 October 2015 |
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