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Formation mechanism and conformational structure of 2,3,4-trimethyl-1,5-di(thiophen-2-yl)pentane-1,5-dione: quantum chemical study

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Abstract

The mechanism of formation of 1,5-diketone, a key intermediate in the stereoselective assembly of 2,3,4-trimethyl-7-methylidene-1,5-di(thiophen-2-yl)-6,8-dioxabicyclo[3.2.1]octane, and the conformational structures of the reagents and products were studied by quantum chemical calculations at the MP2/6-311++G**//B3LYP/6-31G* level of theory with solvent effects treated within the polarizable continuum model. The activation barrier for the addition of the 1-oxo-1-(thiophen-2-yl)propan-2-ide ion (1), which is generated from 1-(thiophen-2-yl)propan-1-one, to acetylene is 15.2 kcal mol–1. The reaction affords β,γ-unsaturated ketone. The subsequent addition of carbanion 1 to the C=C double bond of the resulting β,γ-unsaturated ketons yields 1,5-diketone and occurs with insignificant (less than 1 kcal mol–1) activation barrier.

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Authors and Affiliations

  1. Irkutsk State University, 1 ul. K. Marksa, 664033, Irkutsk, Russian Federation

    N. M. Vitkovskaya & V. B. Kobychev

  2. East-Siberian Institute of the Ministry of Internal Affairs of the Russian Federation, 110 ul. Lermontova, 664074, Irkutsk, Russian Federation

    E. Yu. Larionova

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

    E. Yu. Shmidt & B. A. Trofimov

Authors
  1. N. M. Vitkovskaya
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  2. E. Yu. Larionova
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  3. V. B. Kobychev
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  4. E. Yu. Shmidt
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  5. B. A. Trofimov
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Correspondence to N. M. Vitkovskaya.

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Dedicated to Academician of the Russian Academy of Sciences N. S. Zefirov on the occasion of his 80th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 0394—0400, February, 2016.

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Vitkovskaya, N.M., Larionova, E.Y., Kobychev, V.B. et al. Formation mechanism and conformational structure of 2,3,4-trimethyl-1,5-di(thiophen-2-yl)pentane-1,5-dione: quantum chemical study. Russ Chem Bull 65, 394–400 (2016). https://doi.org/10.1007/s11172-016-1311-5

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  • DOI: https://doi.org/10.1007/s11172-016-1311-5

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