Dupuy Stéphanie, Crawford Luke, Bühl Michael, Nolan Steven P
EastCHEM, School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, Fife, KY16 9ST (UK).
Chemistry. 2015 Feb 16;21(8):3399-408. doi: 10.1002/chem.201405716. Epub 2015 Jan 7.
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.
本文描述了金催化的原脱羧反应的机理研究。每个反应步骤都已通过实验和计算进行了研究。更具体地说，脱羧步骤的活化参数已通过动力学研究确定。对芳基金中间体水解的进一步实验研究表明，在高转化率下，原金化反应可能会与脱羧过程竞争。已表明这种限速步骤的转变与pKa有关。这些研究得到了密度泛函理论（DFT）计算的支持，有助于更好地理解反应机理的哪些普遍特征导致了脱羧过程。
