Rate and Equilibrium Constants for the Addition of N-Heterocyclic Carbenes into Benzaldehydes: A Remarkable 2-Substituent Effect**

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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 p...

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Detalles Bibliográficos
Autores principales: Collett, Christopher J, Massey, Richard S, Taylor, James E, Maguire, Oliver R, O'Donoghue, AnnMarie C, Smith, Andrew D
Formato: Online Artículo Texto
Lenguaje:English
Publicado: WILEY-VCH Verlag 2015
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4510784/
https://www.ncbi.nlm.nih.gov/pubmed/25908493
http://dx.doi.org/10.1002/anie.201501840
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author Collett, Christopher J
Massey, Richard S
Taylor, James E
Maguire, Oliver R
O'Donoghue, AnnMarie C
Smith, Andrew D
author_facet Collett, Christopher J
Massey, Richard S
Taylor, James E
Maguire, Oliver R
O'Donoghue, AnnMarie C
Smith, Andrew D
author_sort Collett, Christopher J
collection PubMed
description 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.
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spelling pubmed-45107842015-07-24 Rate and Equilibrium Constants for the Addition of N-Heterocyclic Carbenes into Benzaldehydes: A Remarkable 2-Substituent Effect** Collett, Christopher J Massey, Richard S Taylor, James E Maguire, Oliver R O'Donoghue, AnnMarie C Smith, Andrew D Angew Chem Int Ed Engl Communications 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. WILEY-VCH Verlag 2015-06-01 2015-04-23 /pmc/articles/PMC4510784/ /pubmed/25908493 http://dx.doi.org/10.1002/anie.201501840 Text en © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. http://creativecommons.org/licenses/by/3.0/ 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.
spellingShingle Communications
Collett, Christopher J
Massey, Richard S
Taylor, James E
Maguire, Oliver R
O'Donoghue, AnnMarie C
Smith, Andrew D
Rate and Equilibrium Constants for the Addition of N-Heterocyclic Carbenes into Benzaldehydes: A Remarkable 2-Substituent Effect**
title Rate and Equilibrium Constants for the Addition of N-Heterocyclic Carbenes into Benzaldehydes: A Remarkable 2-Substituent Effect**
title_full Rate and Equilibrium Constants for the Addition of N-Heterocyclic Carbenes into Benzaldehydes: A Remarkable 2-Substituent Effect**
title_fullStr Rate and Equilibrium Constants for the Addition of N-Heterocyclic Carbenes into Benzaldehydes: A Remarkable 2-Substituent Effect**
title_full_unstemmed Rate and Equilibrium Constants for the Addition of N-Heterocyclic Carbenes into Benzaldehydes: A Remarkable 2-Substituent Effect**
title_short Rate and Equilibrium Constants for the Addition of N-Heterocyclic Carbenes into Benzaldehydes: A Remarkable 2-Substituent Effect**
title_sort rate and equilibrium constants for the addition of n-heterocyclic carbenes into benzaldehydes: a remarkable 2-substituent effect**
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4510784/
https://www.ncbi.nlm.nih.gov/pubmed/25908493
http://dx.doi.org/10.1002/anie.201501840
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