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Alkyland arylketone reactions with phenylacetylene promoted by KOH—DMSO superbase: a quantum chemical study

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Abstract

Mechanisms of ethynylation and vinylation of ketones with phenylacetylene in the presence of KOH•5DMSO superbase were studied using the MP2/6-311++G**//B3LYP/6-31+G* approach. The thermal effects and activation barriers to individual reaction stages were evaluated. It was shown that stereoscpecificity of ketone vinylation with PhC≡CH is due to the possibility of isomerization of both carbanion intermediates and enolate anions originating from the final β,γ-unsaturated ketones. The calculated activation energies of the vinylation of substituted ketones are in good agreement with the experimentally observed differences in their reactivity with respect to the addition of phenylacetylene.

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Authors and Affiliations

  1. Irkutsk State University, 1 ul. Karla Marksa, 664003, Irkutsk, Russian Federation

    V. B. Kobychev, N. M. Vitkovskaya & V. B. Orel

  2. A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 ul. Favorskogo, 664033, Irkutsk, Russian Federation

    E. Yu. Schmidt & B. A. Trofimov

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  1. V. B. Kobychev
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  2. N. M. Vitkovskaya
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  3. V. B. Orel
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  4. E. Yu. Schmidt
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  5. B. A. Trofimov
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Correspondence to V. B. Kobychev.

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Dedicated to Academician of the Russian Academy of Sciences V. I. Minkin on the occasion of his 80th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0518—0524, March, 2015.

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Kobychev, V.B., Vitkovskaya, N.M., Orel, V.B. et al. Alkyland arylketone reactions with phenylacetylene promoted by KOH—DMSO superbase: a quantum chemical study. Russ Chem Bull 64, 518–524 (2015). https://doi.org/10.1007/s11172-015-0895-5

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  • DOI: https://doi.org/10.1007/s11172-015-0895-5

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