1. The Gold(I)‐Catalysed Protodecarboxylation Mechanism
- Author
-
Stéphanie Dupuy, Steven P. Nolan, Michael Bühl, Luke Crawford, European Research Council, University of St Andrews. School of Chemistry, and University of St Andrews. EaSTCHEM
- Subjects
Decarboxylation ,Organic Chemistry ,Quinoline ,NDAS ,General Chemistry ,QD Chemistry ,Catalysis ,N-heterocycle carbenes ,chemistry.chemical_compound ,chemistry ,Organic chemistry ,Protodeauration ,QD ,Gold ,Mechanism ,Mechanism (sociology) - Abstract
The authors thank the EPSRC and the ERC (FUNCAT) for funding. S.P.N. is a Royal Society Wolfson Merit Award holder. 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. Postprint
- Published
- 2015