On the mechanism of the digold(I) hydroxide-catalyzed hydrophenoxylation of alkynes

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Gomez-Suarez, Adrian and Oonishi, Yoshihiro and Martin, Anthony R. and Vummaleti, Sai V. C. and Nelson, David J. and Cordes, David B. and Slawin, Alexandra M. Z. and Cavallo, Luigi and Nolan, Steven P. and Poater, Albert (2016) On the mechanism of the digold(I) hydroxide-catalyzed hydrophenoxylation of alkynes. Chemistry - A European Journal, 22 (3). pp. 1125-1132. ISSN 1521-3765 (https://doi.org/10.1002/chem.201503097)

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Abstract

Herein we present a detailed investigation of the mechanistic aspects of the dual gold-catalysed hydrophenoxylation of alkynes, using both experimental and computational methods. The dissociation of [{Au(NHC)}2(µ-OH)][BF4] is essential to enter the catalytic cycle; this step is favored in the presence of bulky, non-coordinating counterions. Moreover, in silico studies confirmed that phenol does not only act as a reactant, but as a co-catalyst, lowering the energy barriers for 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.

ORCID iDs

Gomez-Suarez, Adrian, Oonishi, Yoshihiro, Martin, Anthony R., Vummaleti, Sai V. C., Nelson, David J. ORCID logoORCID: https://orcid.org/0000-0002-9461-5182, Cordes, David B., Slawin, Alexandra M. Z., Cavallo, Luigi, Nolan, Steven P. and Poater, Albert;
  • Item type:Article
    ID code:54558
    Dates:
    Date
    Event
    18 January 2016
    Published
    11 December 2015
    Published Online
    12 October 2015
    Accepted
    Notes:This is the peer reviewed version of the following article:Gomez-Suarez, A., Oonishi, Y., Martin, A. R., Vummaleti, S. V. C., Nelson, D. J., Cordes, D. B., ... Poater, A. (2015). On the mechanism of the digold(I) hydroxide-catalyzed hydrophenoxylation of alkynes. Chemistry - A European Journal, which has been published in final form at: http://dx.doi.org/10.1002/chem.201503097. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:13 Oct 2015 13:22
    Last modified:11 Nov 2024 11:12
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/54558
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