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Reactions of heterocumulenes with organometallic reagents: XIV. Quantum-chemical study on the mechanism of unusual thermally induced transformation of methyl N-Methylbuta-2,3-dienimidothioates into iminocyclobutenes with migration of the methylsulfanyl group

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Abstract

The mechanism of formation of cyclobutene ring from methyl 2-methoxy-and 2-phenyl-N-methylbuta-2,3-dienimidothioates (H2C=C=C(R)-C(SMe)=NMe, 1-aza-1,3,4-trienes) was studied by quantum-chemical methods. The limiting stage in the [1,3]-sigmatropic migration of the methylsulfanyl group was found to follow a reaction path involving a “collapsed” state of the azatriene with linear configuration of the C=N-Me fragment, which is characterized by reduced activation barrier. The results of calculations substantiate preferential formation of pyrrole and dihydropyridine heterorings in the thermolysis of methyl 2-methoxy-N-methylbuta-2,3-dienimidothioate and of dihydropyridine and cyclobutene structures in the thermolysis of methyl N-methyl-2-phenylbuta-2,3-dienimidothioate.

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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 & O. A. Tarasova

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  1. V. A. Shagun
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  2. N. A. Nedolya
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  3. O. A. Tarasova
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Correspondence to V. A. Shagun.

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Original Russian Text © V.A. Shagun, N.A. Nedolya, O.A. Tarasova, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 11, pp. 1601–1608.

For communication XIII, see [1].

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Shagun, V.A., Nedolya, N.A. & Tarasova, O.A. Reactions of heterocumulenes with organometallic reagents: XIV. Quantum-chemical study on the mechanism of unusual thermally induced transformation of methyl N-Methylbuta-2,3-dienimidothioates into iminocyclobutenes with migration of the methylsulfanyl group. Russ J Org Chem 43, 1595–1603 (2007). https://doi.org/10.1134/S1070428007110024

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  • DOI: https://doi.org/10.1134/S1070428007110024

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