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Reactions of heterocumulenes with organometallic reagents: XI. Quantum-chemical study on the mechanism of noncatalytic cyclization of methyl 2-methoxy-N-methylbuta-2,3-dienimidothioate (1-aza-1,3,4-triene) into substituted pyrrole

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Abstract

Rotational isomerism of methyl 2-methoxy-N-methylbuta-2,3-dienimidothioate (1-aza-1,3,4-triene), which is readily available from 1-lithio-1-methoxyallene, methyl isothiocyanate, and methyl iodide, was studied by quantum-chemical methods. Four most stable rotamers with the energies of activation of their mutual transformations exceeding 35 kJ/mol were identified. The potential energy surfaces for the formation of pyrrole structure from 1-aza-1,3,4-triene via different ring closure channels were analyzed. According to the results of calculations, the most probable is direct [1,5]-cyclization of 1-aza-1,3,4-triene through a cyclic carbene species.

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Authors and Affiliations

  1. Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, ul. Favorskogo 1, Irkutsk, 664033, Russia

    V. A. Shagun & N. A. Nedolya

  2. Utrecht University, Utrecht, The Netherlands

    L. Brandsma

Authors
  1. V. A. Shagun
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  2. N. A. Nedolya
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  3. L. Brandsma
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Original Russian Text © V.A. Shagun, N.A. Nedolya, L. Brandsma, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 4, pp. 578–589.

For communication X, see [1].

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Shagun, V.A., Nedolya, N.A. & Brandsma, L. Reactions of heterocumulenes with organometallic reagents: XI. Quantum-chemical study on the mechanism of noncatalytic cyclization of methyl 2-methoxy-N-methylbuta-2,3-dienimidothioate (1-aza-1,3,4-triene) into substituted pyrrole. Russ J Org Chem 43, 576–586 (2007). https://doi.org/10.1134/S107042800704015X

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  • DOI: https://doi.org/10.1134/S107042800704015X

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