The gold(I)-catalysed protodecarboxylation mechanism
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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.
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 . DOI: 10.1002/chem.201405716
Chemistry - A European Journal
© 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
DescriptionThe 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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