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

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.

Citation
Gómez-Suárez A, Oonishi Y, Martin AR, Vummaleti SVC, Nelson DJ, et al. (2015) On the Mechanism of the Digold(I)-Hydroxide-Catalysed Hydrophenoxylation of Alkynes. Chem Eur J 22: 1125–1132. Available: http://dx.doi.org/10.1002/chem.201503097.

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).

Publisher
Wiley

Journal
Chemistry - A European Journal

DOI
10.1002/chem.201503097

PubMed ID
26662656

Additional Links
http://onlinelibrary.wiley.com/doi/10.1002/chem.201503097/full
https://strathprints.strath.ac.uk/54558/1/Gomez_Suarez_etal_CEJ_2015_On_the_mechanism_of_the_digold_I_hydroxide_catalyzed.pdf

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