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Heterocumulenes reactions with organometallic reagents: XXI. Quantum-chemical study of structural transformations of 2-methoxy- and 2-(methylsulfanyl)-N-methylbuta-2,3-dienimidothioates in the Presence of cubr: Pyrrole or methyl-3-(methylsulfanyl)but-2-enimidothioate?

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Abstract

Utilizing the MP2/6-31G(d,p) method a quantum-chemical investigation was performed of processes catalyzed by CuBr leading to the formation of pyrrole structures from methyl-2 methoxy- and methyl 2-(methylsulfanyl)-N-methylbuta-2,3-dienimidothioates (1-aza-1,3,4-trienes). According to calculations 1-aza-1,3,4-trienes may form highly stable adducts with CuBr owing to the coordination bonding of the copper atom with the π-system (C=C=C) and/or heteroatoms (N, S, O). The main channel of the structural reorganization of the CuBr adduct with methoxy-substituted 1-aza-1,3,4-triene is the thermodynamically controlled formation of the pyrrole ring. In the 3-(methylsulfanyl)-1-aza-1,3,4-triene CuBr initiates the cleavage of the C-S bond in the imidothioate fragment (MeS-C=N-Me) and the kinetically controlled formation of methyl N-methyl-2,3-bis(methylsulfanyl) but-2-enimidothioate.

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Authors and Affiliations

  1. Faworsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, 664033, Russia

    V. A. Shagun & N. A. Nedolya

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  1. V. A. Shagun
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  2. N. A. Nedolya
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Correspondence to V. A. Shagun.

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Original English Text © V.A. Shagun, N.A. Nedolya, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 11, pp. 1655–1664.

For Communication XX, see [1]

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Shagun, V.A., Nedolya, N.A. Heterocumulenes reactions with organometallic reagents: XXI. Quantum-chemical study of structural transformations of 2-methoxy- and 2-(methylsulfanyl)-N-methylbuta-2,3-dienimidothioates in the Presence of cubr: Pyrrole or methyl-3-(methylsulfanyl)but-2-enimidothioate?. Russ J Org Chem 49, 1637–1646 (2013). https://doi.org/10.1134/S1070428013110134

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