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

journal contribution
posted on 2023-05-17, 15:06 authored by Alireza AriafardAlireza Ariafard, Asadollah, E, Ostadebrahim, M, Rajabi, NA, Brian YatesBrian Yates
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.

History

Publication title

Journal of the American Chemical Society

Volume

134

Issue

40

Pagination

16882-16890

ISSN

0002-7863

Department/School

School of Natural Sciences

Publisher

Amer Chemical Soc

Place of publication

1155 16Th St, Nw, Washington, USA, Dc, 20036

Rights statement

Copyright 2012 American Chemical Society

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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