Jump to main content
Jump to site search


The preference for dual-gold(I) catalysis in the hydro(alkoxylation vs phenoxylation) of alkynes

Abstract

Dinuclear gold complexes and their use in catalysis have received significant recent attention, but there are few critical comparisons of mono- versus dual gold-catalysed pathways. Herein we study the hydroalkoxylation and hydrophenoxylation of alkynes using density functional theory calculations, and compare two possible mechanisms that have been proposed previously on the basis of theoretical and experimental studies, which unravel different preferences because of both the nature of the alkyne and alcohol, as well as the non-innocent role of the counter-anion of the dual gold based catalyst. Entropy is found to have a significant effect, rendering the nucleophilic attack of the monoaurated intermediate [Au(L)(η2-alkyne)]+ difficult both kinetically and thermodynamically; this mechanism cannot easily form only the trans-alkene product that is observed experimentally. Instead, reaction via a dual gold catalysed mechanism presents much lower barriers. In addition, for the sake of direct comparison with recent results by Belanzoni, Zuccaccia, oversimplification of the N-heterocyclic carbene (NHC) ligand in the calculations might decrease the enthalpy barrier and lead to results that are not directly applicable to experiment. Moreover, the alkylic or arylic nature of the alkyne and/or alcohol is also tested.

Back to tab navigation

Supplementary files

Publication details

The article was received on 15 Jun 2017, accepted on 10 Jul 2017 and first published on 10 Jul 2017


Article type: Paper
DOI: 10.1039/C7OB01457K
Citation: Org. Biomol. Chem., 2017, Accepted Manuscript
  •   Request permissions

    The preference for dual-gold(I) catalysis in the hydro(alkoxylation vs phenoxylation) of alkynes

    È. Casals-Cruañas, O. F. Gonzalez-Belman, P. Besalú-Sala, D. J. Nelson and A. Poater, Org. Biomol. Chem., 2017, Accepted Manuscript , DOI: 10.1039/C7OB01457K

Search articles by author

Spotlight

Advertisements