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The Gold(I)‐Catalysed Protodecarboxylation Mechanism
Author(s) -
Dupuy Stéphanie,
Crawford L. Ellis,
Bühl Michael,
Nolan Steven P.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201405716
Subject(s) - decarboxylation , limiting , rate determining step , chemistry , mechanism (biology) , reaction mechanism , kinetic energy , two step , computational chemistry , hydrolysis , process (computing) , combinatorial chemistry , stereochemistry , thermodynamics , catalysis , organic chemistry , computer science , physics , mechanical engineering , quantum mechanics , engineering , operating system
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 p K a ‐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.