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Reactions of heterocumulenes with organometallic reagents: XXII. Quantum chemical study of structural transformations of benzylsulfanyl-substituted 2-aza-1,3,5-triene by the action of superbases. Concurrent formation of 4,5-dihydro-3H-azepine and 4,5-dihydro-1,3-thiazole

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Abstract

The formation of 4,5-dihydro-3H-azepine and/or 4,5-dihydro-1,3-thiazole structures in the reaction of 1-(benzylsulfanyl)-2-methoxy-N-(propan-2-ylidene)buta-1,3-dien-1-amine (2-aza-1,3,5-triene) with potassium tert-butoxide or lithium diisopropylamide has been analyzed by B3LYP/6-31G(d,p) quantum chemical calculations. According to the calculations, the reaction with potassium tert-butoxide gives 4,5-dihydro-3H-azepine and 4,5-dihydro-1,3-thiazole derivatives with almost equal probabilities, whereas lithium diisopropylamide clearly favors the formation of thiazole ring.

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Authors and Affiliations

  1. Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, ul. Favorskogo 1, 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 N. A. Nedolya.

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Original Russian Text © V.A. Shagun, N.A. Nedolya, 2015, published in Zhurnal Organicheskoi Khimii, 2015, Vol. 51, No. 4, pp. 521–529.

For communication XXI, see [1].

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Shagun, V.A., Nedolya, N.A. Reactions of heterocumulenes with organometallic reagents: XXII. Quantum chemical study of structural transformations of benzylsulfanyl-substituted 2-aza-1,3,5-triene by the action of superbases. Concurrent formation of 4,5-dihydro-3H-azepine and 4,5-dihydro-1,3-thiazole. Russ J Org Chem 51, 504–512 (2015). https://doi.org/10.1134/S1070428015040077

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  • DOI: https://doi.org/10.1134/S1070428015040077

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