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Issue 103, 2015
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Computational insight into the mechanism of the Pd(0)–Brønsted acid cooperatively catalysed head-to-tail dimerization of terminal alkynes

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Abstract

The Pd(0)–Brønsted acid cooperatively catalysed head-to-tail dimerization of terminal alkynes was computationally studied to gain a mechanistic insight. In the presence of the Brønsted acid (Ph2P(O)OH), the formation of a hydridopalladium intermediate via the oxidative addition (OA) of the terminal alkyne Csp–H bond into the Pd(0) centre might not be a favourable reaction pathway. Instead, after the coordination of the Brønsted acid with the Pd(0)–alkyne complex, a proton transfer reaction from the acid to the terminal carbon of the alkyne in a concerted manner is found to be a favourable pathway, leading to the alkenyl(Ph2P(O)O)Pd(II) intermediate. The alternative route that the proton transfer to the internal carbon of alkyne, however, is less competitive. Computational findings suggest that the terminal carbon of the alkyne has more negative charge, and therefore, is more ready to be protonated than the internal carbon in the presence of the Brønsted acid. The regio-selectivity for the proton transfer step is also responsible for the exclusive formation of the head-to-tail dimerization product.

Graphical abstract: Computational insight into the mechanism of the Pd(0)–Brønsted acid cooperatively catalysed head-to-tail dimerization of terminal alkynes

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Publication details

The article was received on 17 Jul 2015, accepted on 30 Sep 2015 and first published on 07 Oct 2015


Article type: Paper
DOI: 10.1039/C5RA14086B
Citation: RSC Adv., 2015,5, 84636-84642

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    Computational insight into the mechanism of the Pd(0)–Brønsted acid cooperatively catalysed head-to-tail dimerization of terminal alkynes

    H. Zhang and X. Bao, RSC Adv., 2015, 5, 84636
    DOI: 10.1039/C5RA14086B

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