A MEDT STUDY OF THE MECHANISM AND SELECTIVITY OF THE HETERO-DIELS–ALDER REACTION BETWEEN 3-BENZOYLPYRROLO[1,2-<i>c</i>][1,4]-BENZOXAZINE-1,2,4-TRIONE AND VINYL ACETATE

Authors

  • Ameur Soukaina Molecular Modeling and Spectroscopy Research Team, Faculty of Science, Chouaïb Doukkali University, P. O. Box 20, 24000 El Jadida Laboratory of Bioorganic Chemistry, Department of Chemistry Faculty of Sciences, Chouaïb Doukkali University, P. O. Box 20, 24000 El Jadida
  • Ali Barhoumi Molecular Modeling and Spectroscopy Research Team, Faculty of Science, Chouaïb Doukkali University, P. O. Box 20, 24000 El Jadida
  • Mar Ríos-Gutiérrez Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, 46100 Burjassot, Valencia
  • Anas Ouled Aitouna Molecular Modeling and Spectroscopy Research Team, Faculty of Science, Chouaïb Doukkali University, P. O. Box 20, 24000 El Jadida Laboratory of Bioorganic Chemistry, Department of Chemistry Faculty of Sciences, Chouaïb Doukkali University, P. O. Box 20, 24000 El Jadida
  • Habib El Alaoui El Abdallaoui Molecular Modeling and Spectroscopy Research Team, Faculty of Science, Chouaïb Doukkali University, P. O. Box 20, 24000 El Jadida
  • Noureddine Mazoir Laboratory of Bioorganic Chemistry, Department of Chemistry Faculty of Sciences, Chouaïb Doukkali University, P. O. Box 20, 24000 El Jadida
  • Mohammed Elalaoui Belghiti Laboratory of Physical Chemistry of Materials, Ben M'Sick Faculty of Sciences, Hassan II University, Casablanca Laboratory of Nernest Technology, 163 Willington Street, Sherbrooke, QC J1H5C7
  • Asad Syed Department of Botany and Microbiology, College of Science, King Saud University, P. O. Box 2455 Riyadh 11451
  • Abdellah Zeroual Molecular Modeling and Spectroscopy Research Team, Faculty of Science, Chouaïb Doukkali University, P. O. Box 20, 24000 El Jadida
  • Luis R. Domingo Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, 46100 Burjassot, Valencia

DOI:

https://doi.org/10.1007/7267

Keywords:

chemoselectivity, DFT calculations, hetero-Diels–Alder reaction, MEDT

Abstract

The chemo-, regio-, and stereoselectivity of the hetero-Diels–Alder reaction between 3-benzoylpyrrolo[1,2-c][1,4]benzoxazine-1,2,4-trione and vinyl acetate, has been investigated within molecular electron density theory at the B3LYP/6-311(d,p) level of theory. The conceptual density functional theory reactivity indices, as well as the activation and reaction energies have been analyzed, and five possible reaction paths for this cycloaddition reaction, resulting from the presence of three heterodiene frameworks in the molecule of the diene reactant have been studied. The conceptual density functional theory analysis indicates that vinyl acetate acts as a nucleophile and 3-benzoylpyrrolo[1,2-c][1,4]benzoxazine-1,2,4-trione acts as a strong electrophile. The computed activation and reaction energies reveal that that this reaction is chemo-, stereo-, and regioselective, which is consistent with the experimental findings. Topological electron localization function analysis was used to look into how the electron densities were reorganized along the preferred reaction path. According to this analysis, the reaction takes place through a two-stage one-step mechanism.

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Published

2023-04-11

Issue

Vol. 59 No. 3 (2023): Cycloaddition reactions: recent progress

Section

Original Papers