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Quantum mechanical modeling unveils the effect of substitutions on the activation barriers of the Diels–Alder reactions of an antiviral compound 7H-benzo[a]phenalene

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Abstract

Density functional theory has been utilized for exploring the mechanism of Diels–Alder reaction between 7H-benzo[a]phenalene and maleic anhydride. 7H-Benzo[a]phenalene is an antiviral compound, and information available about its cycloaddition reactions with possible reaction path and mechanism is scarce. In order to work on the synthesis of its further potential derivatives, the mechanism of its reaction with all aspects should be well understood. Five novel intermediates involved in this reaction are reported in this work. Diels–Alder reaction of maleic anhydride has found many applications in the synthesis of wide range of useful products. One of the major concerns of this work is to evaluate the consequences of introducing electron donating and electron withdrawing substituents on the reactivity of maleic anhydride towards 7H-benzo[a]phenalene. Thermodynamic parameters, activation parameters, energies of frontier orbitals, global reactivity indices and global electron density transfer (GEDT) have been determined for all the reactions. Fukui functions are computed for each reactant in order to identify the most reactive sites. All the reactions have been found to proceed via normal electron demand having polar nature. The substituents with opposite electronic properties were expected to affect the reactivity of dienophile in an inverse manner; however, the results are not according to this assumption. Rather, both kinds of substituents increased the activation barrier of the reaction. This behavior has been explained in the light of various parameters such as the stability of reacting species and gap of frontier molecular orbitals. Experimental studies reported previously are in agreement with these results.

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Funding

A.M. is grateful to Higher Education Commission (HEC) Pakistan for providing financial support for this study (NRPU/5613).

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  1. Department of Chemistry, Government College University Faisalabad, Faisalabad, 38000, Pakistan

    Umatur Rehman, Asim Mansha & Ameer Fawad Zahoor

  2. Department of Chemistry, University of Agriculture Faisalabad, Faisalabad, 38040, Pakistan

    Muhammad Zahid

  3. Department of Chemistry, Government College Women University Faisalabad, Faisalabad, Pakistan

    Sadia Asim & Zulfiqar Ahmad Rehan

Authors
  1. Umatur Rehman
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  2. Asim Mansha
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  3. Muhammad Zahid
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  4. Sadia Asim
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  5. Ameer Fawad Zahoor
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  6. Zulfiqar Ahmad Rehan
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Contributions

All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by UR, AM, MZ, SA and ZAR. The first draft of the manuscript was written by AFZ, AM, and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

Corresponding authors

Correspondence to Asim Mansha or Ameer Fawad Zahoor.

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Rehman, U., Mansha, A., Zahid, M. et al. Quantum mechanical modeling unveils the effect of substitutions on the activation barriers of the Diels–Alder reactions of an antiviral compound 7H-benzo[a]phenalene. Struct Chem 33, 1907–1920 (2022). https://doi.org/10.1007/s11224-022-01948-6

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  • DOI: https://doi.org/10.1007/s11224-022-01948-6

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