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

Adrián Gómez-Suárez, Yoshihiro Oonishi, Anthony R. Martin, Sai V. C. Vummaleti, David J. Nelson, David B. Cordes, Alexandra M. Z. Slawin, Luigi Cavallo, Steven P. Nolan, Albert Poater

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Abstract

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Original languageEnglish (US)
Pages (from-to)1125-1132
Number of pages8
JournalChemistry - A European Journal
Volume22
Issue number3
DOIs
StatePublished - Dec 13 2015

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: The ERC (Advanced Investigator Award-FUNCAT), EPSRC, and Syngenta are gratefully acknowledged for support. Umicore AG is acknowledged for their generous gift of materials. S.P.N. and L.C. thank the King Abdullah University of Science and Technology (CCF project) for support. Y.O. thanks the Uehara Memorial Foundation for a Research Fellowship. 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).

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