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

Adrián Gõmez-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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

37 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)1125-1132
Number of pages8
JournalChemistry - A European Journal
Volume22
Issue number3
Early online date11 Dec 2015
DOIs
Publication statusPublished - 18 Jan 2016

Keywords

  • Alkynes
  • Density functional calculations
  • Gold
  • Homogeneous catalysis
  • Hydrophenoxylation
  • Reaction mechanisms

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