Rate and equilibrium constants for the addition of N-Heterocyclic Carbenes into benzaldehydes : a remarkable 2-substituent effect
Abstract
Rate and equilibrium constants for the reaction between N-aryl triazolium 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.
Citation
Collett , 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 , vol. 54 , no. 23 , pp. 6887-6892 . DOI: 10.1002/anie.201501840
Publication
Angewandte Chemie International Edition
Status
Peer reviewed
ISSN
1433-7851Type
Journal article
Rights
Copyright 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.
Description
We thank the Royal Society for a University Research Fellowship (ADS), the EPSRC (CJC and RM) grant number EP/G013268/1 and the European Research Council under the European Union's Seventh Framework Programme (FP7/2007-2013) ERC grant agreement no 279850 (JET). We also thank the EPSRC UK National Mass Spectrometry Facility at Swansea University.Collections
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