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The gold(I)-catalysed protodecarboxylation mechanism

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Nolan_2015_ChemEUJ_GoldCatalysed_AM.pdf (1.174Mb)
Date
16/02/2015
Author
Dupuy, Stephanie
Crawford, Luke
Buehl, Michael
Nolan, Steven Patrick
Funder
European Research Council
Grant ID
FP7-227817 FUNCAT
Keywords
Decarboxylation
Gold
Mechanism
N-heterocycle carbenes
Protodeauration
QD Chemistry
NDAS
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Abstract
A mechanistic study of the gold-catalysed protodecarboxylation is described. Each reaction step has been investigated experimentally and computationally. More specifically, the activation parameters for the decarboxylation step have been determined through kinetic studies. Further experimental studies on the hydrolysis of the arylgold intermediate have revealed that the protodeauration can become competitive with the decarboxylation process at high conversions. This switch in rate-limiting step has been shown to be pKa-dependent. These studies have been supported by DFT calculations and permit a better understanding of which prevalent features of the reaction mechanism account for the decarboxylation process.
Citation
Dupuy , S , Crawford , L , Buehl , M & Nolan , S P 2015 , ' The gold(I)-catalysed protodecarboxylation mechanism ' , Chemistry - A European Journal , vol. 21 , no. 8 , pp. 3399-3408 . https://doi.org/10.1002/chem.201405716
Publication
Chemistry - A European Journal
Status
Peer reviewed
DOI
https://doi.org/10.1002/chem.201405716
ISSN
0947-6539
Type
Journal article
Rights
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This is the accepted version of the following article: Dupuy, S., Crawford, L., Bühl, M. and Nolan, S. P. (2015), The Gold(I)-Catalysed Protodecarboxylation Mechanism. Chem. Eur. J., 21: 3399–3408, which has been published in final form at http://dx.doi.org/10.1002/chem.201405716
Description
The authors thank the EPSRC and the ERC (FUNCAT) for funding. S.P.N. is a Royal Society Wolfson Merit Award holder.
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  • University of St Andrews Research
URL
http://onlinelibrary.wiley.com/doi/10.1002/chem.201405716/suppinfo
URI
http://hdl.handle.net/10023/7985

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