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

Adrian Gomez-Suarez, 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, 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.
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

  • gold catalysis
  • hydrophenoxylation of alkynes
  • alkynes
  • nucleophiles

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11 Citations (Scopus)
9 Downloads (Pure)

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