Theoretical investigation into the mechanism of Au(I)-catalyzed reaction of alcohols with 1,5 enynes

Alireza Ariafard, Esmat Asadollah, Maryam Ostadebrahim, Nasir Ahmad Rajabi, Brian F. Yates

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

Density functional theory has been used to investigate the reactions of 1,5 enynes with alcohols in the presence of a gold catalyst. We have compared the mechanism of the alcohol addition reaction for the enyne with that of the enyne where the carbon at position 3 is replaced with silicon. We find that different intermediates are present in both cases, and in the case of the silicon analogue, the intermediate that we find from the calculations is different from any that have previously been proposed in the literature. For the silicon analogue we have been able to rationalize the observed effects of alcohol concentration and nucleophilicity on the product distribution. For the carbon-based enyne we have shown why different products are observed depending on the substitution at position 3 of the enyne. Overall, we have provided for the first time a consistent explanation and rationalization of several different experiments that have been previously published in the literature. Our mechanism will assist in predicting the outcome of experimental reactions involving different alcohols, reagent concentrations, and substitution patterns of the 1,5 enynes.

Original languageEnglish
Pages (from-to)16882-16890
Number of pages9
JournalJournal of the American Chemical Society
Volume134
Issue number40
Early online date19 Sep 2012
DOIs
Publication statusPublished - 10 Oct 2012

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Theoretical investigation into the mechanism of Au(I)-catalyzed reaction of alcohols with 1,5 enynes. / Ariafard, Alireza; Asadollah, Esmat; Ostadebrahim, Maryam; Rajabi, Nasir Ahmad; Yates, Brian F.

In: Journal of the American Chemical Society, Vol. 134, No. 40, 10.10.2012, p. 16882-16890.

Research output: Contribution to journalArticle

Ariafard, Alireza ; Asadollah, Esmat ; Ostadebrahim, Maryam ; Rajabi, Nasir Ahmad ; Yates, Brian F. / Theoretical investigation into the mechanism of Au(I)-catalyzed reaction of alcohols with 1,5 enynes. In: Journal of the American Chemical Society. 2012 ; Vol. 134, No. 40. pp. 16882-16890.
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