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Journal of Chemistry
Volume 2015, Article ID 430358, 8 pages
http://dx.doi.org/10.1155/2015/430358
Research Article

Copper-Catalyzed Eglinton Oxidative Homocoupling of Terminal Alkynes: A Computational Study

Departament de Química Inorgànica i Institut de Recerca de Química Teòrica i Computacional, Universitat de Barcelona, Avinguda Diagonal 645, 08028 Barcelona, Spain

Received 30 September 2015; Revised 24 November 2015; Accepted 6 December 2015

Academic Editor: Bartolo Gabriele

Copyright © 2015 Jesús Jover. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

The copper(II) acetate mediated oxidative homocoupling of terminal alkynes, namely, the Eglinton coupling, has been studied with DFT methods. The mechanism of the whole reaction has been modeled using phenylacetylene as substrate. The obtained results indicate that, in contrast to some classical proposals, the reaction does not involve the formation of free alkynyl radicals and proceeds by the dimerization of copper(II) alkynyl complexes followed by a bimetallic reductive elimination. The calculations demonstrate that the rate limiting-step of the reaction is the alkyne deprotonation and that more acidic substrates provide faster reactions, in agreement with the experimental observations.