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On the Mechanism of the Digold(I)–Hydroxide‐Catalysed Hydrophenoxylation of Alkynes
Author(s) -
GómezSuárez Adrián,
Oonishi Yoshihiro,
Martin Anthony R.,
Vummaleti Sai V. C.,
Nelson David J.,
Cordes David B.,
Slawin Alexandra M. Z.,
Cavallo Luigi,
Nolan Steven P.,
Poater Albert
Publication year - 2016
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.201503097
Subject(s) - catalytic cycle , catalysis , dissociation (chemistry) , chemistry , transition state , hydroxide , phenol , combinatorial chemistry , ion , computational chemistry , organic chemistry
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)][BF 4 ] 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.