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Reactions of Heterocumulenes with Organometallic Reagents: X. Quantum-Chemical Study of the Reaction of Aliphatic Isothiocyanates with Lithiated Allenes. Intramolecular Rearrangements of 1,3,4-Azatrienes

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Abstract

Study of the potential energy surface for the reaction of isothiocyanates with α-lithiated allenes showed that the formation of 1,3,4-azatriene occurs in one step through a four-center transition state. [1,5]-Sigmatropic rearrangements of 1,3,4-azatrienes and electrocyclizations of the resulting conjugated 1,3,5-azatriene systems lead to formation of dihydropyridine ring. Pyrrole structures are more likely to arise from protonation of 3-alkoxy-1,3,4-azatriene.

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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, D-S. D. Toryashinova, N. A. Nedolya & O. A. Tarasova

  2. Utrecht University, Utrecht, the Netherlands

    L. Brandsma

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  1. V. A. Shagun
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  2. D-S. D. Toryashinova
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  3. N. A. Nedolya
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  4. O. A. Tarasova
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  5. L. Brandsma
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Shagun, V.A., Toryashinova, DS.D., Nedolya, N.A. et al. Reactions of Heterocumulenes with Organometallic Reagents: X. Quantum-Chemical Study of the Reaction of Aliphatic Isothiocyanates with Lithiated Allenes. Intramolecular Rearrangements of 1,3,4-Azatrienes. Russian Journal of Organic Chemistry 40, 775–789 (2004). https://doi.org/10.1023/B:RUJO.0000044539.72663.58

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  • DOI: https://doi.org/10.1023/B:RUJO.0000044539.72663.58

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