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Rate and equilibrium constants for the addition of triazolium salt derived N-heterocyclic carbenes to heteroaromatic aldehydes

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Duan_2022_CS_Rate_equilibrium_CC.pdf (1.288Mb)
Date
14/11/2022
Author
Duan, Zhuan
Young, Claire M
Zhu, Jiayun
Slawin, Alexandra
O'Donoghue, AnnMarie Christine
Smith, Andrew D
Funder
EPSRC
Grant ID
EP/S019359
Keywords
QD Chemistry
DAS
MCP
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Abstract
Heteroaromatic aldehydes are often used preferentially or exclusively in a range of NHC-catalysed processes that proceed through the generation of a reactive diaminoenol or Breslow Intermediate (BI), with the reason for their unique reactivity currently underexplored. This manuscript reports measurement of rate and equilibrium constants for the reaction between N-aryl triazolium NHCs and heteroaromatic aldehydes, providing insight into the effect of the NHC and heteroaromatic aldehyde structure up to formation of the BI. Variation in NHC catalyst and heteroaromatic aldehyde structure markedly affect the observed kinetic parameters of adduct formation, decay to starting materials and onward reaction to BI. In particular, large effects are observed with both 3-halogen (Br, F) and 3-methyl substituted pyridine-2-carboxaldehyde derivatives which substantially favour formation of the tetrahedral intermediate relative to benzaldehyde derivatives. Key observations indicate that increased steric hindrance leads to a reduction in both k2 and k−1 for large (2,6-disubstituted)-N-Ar groups within the triazolium scaffold, and sterically demanding aldehyde substituents in the 3-position, but not in the 6-position of the pyridine-2-carboxaldehyde derivatives. As part of this study, the isolation and characterisation of twenty tetrahedral adducts formed upon addition of N-aryl triazolium derived NHCs into heteroaromatic aldehydes are described. These adducts are key intermediates in NHC-catalysed umpolung addition of heteroaromatic aldehydes and are BI precursors.
Citation
Duan , Z , Young , C M , Zhu , J , Slawin , A , O'Donoghue , A C & Smith , A D 2022 , ' Rate and equilibrium constants for the addition of triazolium salt derived N -heterocyclic carbenes to heteroaromatic aldehydes ' , Chemical Science , vol. Advance Article . https://doi.org/10.1039/D2SC05704B
Publication
Chemical Science
Status
Peer reviewed
DOI
https://doi.org/10.1039/D2SC05704B
ISSN
2041-6520
Type
Journal article
Rights
Copyright © The Authors. Open Access. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Description
Authors thank the EPSRC (JZ and CMY, EP/S020713/1 and EP/S019359/1) and ZD (CSC St Andrews PhD studentship) for funding.
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  • University of St Andrews Research
URI
http://hdl.handle.net/10023/26534

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