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On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes

KGaA, Weinheim.Herein, we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes by both experimental and computational methods. The dissociation of [{Au(NHC)}2(μ-OH)][BF4] is essential to enter the catalytic cycle, and this step is favoured by the presence of bulky, non-coordinating counter ions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but also as a co-catalyst, lowering the energy barriers of several transition states. A gem-diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an "off-cycle" rather than an "in-cycle" intermediate

A.P. thanks the Spanish MINECO (project CTQ2014-59832-JIN and FEDER grant UNGI10-4E-801 and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)

© Chemistry - A European Journal, 2016, vol. 22, núm. 3, p. 1125-1132

Wiley

Author: Gómez-Suárez, Adrián
Oonishi, Yoshihiro
Martin, Anthony R.
Vummaleti, Sai Vikrama Chaitanya
Nelson, David J.
Cordes, David B.
Slawin, Alexandra M. Z.
Cavallo, Luigi
Nolan, Steven P.
Poater Teixidor, Albert
Date: 2016 January 18
Abstract: KGaA, Weinheim.Herein, we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes by both experimental and computational methods. The dissociation of [{Au(NHC)}2(μ-OH)][BF4] is essential to enter the catalytic cycle, and this step is favoured by the presence of bulky, non-coordinating counter ions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but also as a co-catalyst, lowering the energy barriers of several transition states. A gem-diaurated species might form during the reaction, but this lies deep within a potential energy well, and is likely to be an "off-cycle" rather than an "in-cycle" intermediate
A.P. thanks the Spanish MINECO (project CTQ2014-59832-JIN and FEDER grant UNGI10-4E-801 and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900)
Format: application/pdf
ISSN: 0947-6539 (versió paper)
1521-3765 (versió electrònica)
Document access: http://hdl.handle.net/10256/13297
Language: eng
Publisher: Wiley
Collection: MINECO/PE 2015-2018/CTQ2014-59832-JIN
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/chem.201503097
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
Is part of: © Chemistry - A European Journal, 2016, vol. 22, núm. 3, p. 1125-1132
Rights: Tots els drets reservats
Subject: Funcional de densitat, Teoria del
Density functionals
Catàlisi homogènia
Homogeneous catalysis
Mecanismes de reacció (Química)
Reaction mechanisms (Chemistry)
Alquins
Alkynes
Title: On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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