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Acid-catalyzed rearrangement of 1-acyl-2-azabuta-1,3-dienes to 4-pyrrolin-2-ones

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Chemistry of Heterocyclic Compounds Aims and scope

1-Acyl-2-azabuta-1,3-dienes underwent rearrangement to 4-pyrrolin-2-ones in the presence of acidic catalysts (silica gel or ZnCl2) and water. The reaction proceeded via the formation of 2,3-dihydroxy-3,4-dihydropyrrole and 2-hydroxy-2Н-pyrrole intermediates, the latter of which was transformed by [1,5]-sigmatropic shift of carbonyl substituent and prototropic isomerization. 4-Chloro-substituted 1-acetyl-2-azabuta-1,3-dienes were stable toward rearrangement, while brominated analogs rearranged into 4-pyrrolin-2-ones, probably as a result of the initial radical hydrodebromination. According to calculations performed at the DFT level, two steps of the reaction were catalyzed by acid: the cyclization of 2-azabutadiene and the sigmatropic shift in the 2-hydroxy-2Н-pyrrole intermediate.

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This work received financial support from the Russian Science Foundation (Project No. 20-13-00044).

The authors would like to express their gratitude to Е. О. Kalinin (Institute of Chemistry, Saint Petersburg State University) for providing the labeled water.

The analysis of obtained compounds and quantumchemical calculations were performed at the Saint Petersburg State University resource centers “Magnetic Resonance Research Center”, “Chemical Analysis and Materials Research Center"“, “Research Center for X-ray Diffraction Studies”, “Chemistry Educational Center”, and “Computing Center”.

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Authors and Affiliations

  1. Institute of Chemistry, Saint Petersburg State University, 7/9 University Embankment, Saint Petersburg, 199034, Russia

    Nikolai V. Rostovskii, Ilia A. Smetanin, Alexander N. Koronatov, Anastasiya V. Agafonova, Vasilii V. Potapenkov, Alexander F. Khlebnikov & Mikhail S. Novikov

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  1. Nikolai V. Rostovskii
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  2. Ilia A. Smetanin
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  3. Alexander N. Koronatov
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  4. Anastasiya V. Agafonova
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  5. Vasilii V. Potapenkov
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  6. Alexander F. Khlebnikov
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  7. Mikhail S. Novikov
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Correspondence to Mikhail S. Novikov.

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Translated from Khimiya Geterotsiklicheskikh Soedinenii, 2020, 56(7), 881–887

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Rostovskii, N.V., Smetanin, I.A., Koronatov, A.N. et al. Acid-catalyzed rearrangement of 1-acyl-2-azabuta-1,3-dienes to 4-pyrrolin-2-ones. Chem Heterocycl Comp 56, 881–887 (2020). https://doi.org/10.1007/s10593-020-02745-x

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