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Effect of hydrogen bonds and CF3 group on the regioselectivity and mechanism of [3 + 2] cycloaddition reactions between nitrile oxide and 2,4-disubstituted cyclopentenes. A MEDT study

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Abstract

The mechanism and the regioselectivity of the non-polar [3 + 2] cycloaddition reactions between nitrile oxide and two cyclopentenes were theoretically investigated within the molecular electron density theory (MEDT) using DFT methods, namely the B3LYP, MPWB1K and ωB97XD functionals together with the standard 6-31G(d) basis set. The activation energies of these 32CA reactions are relatively high, due to the low nucleophilic power of both cycloalkenes and the relatively moderate electrophilic nature of the nitrile oxide. The B3LYP and MPWB1K functionals reproduced high relative energies values, while the ωB97XD one yields better values in the kinetic and thermodynamic energies. The completely 4-regioselectivity that observed experimentally has been explained by the analysis of the relative energies, in which the formation of 4-regioismeric cycloadducts is always the more kinetically favored one. The electron localization function (ELF) topological analysis showed that the studied 32CA reactions proceed through two-stage one-step nonconcerted mechanism. The effects of the hydrogen bonds on the regioselectivity determination have been investigated by mean both noncovalent interactions (NCI) and quantum theory of atoms in molecule (QTAIM) analyses, which confirm the presence of high strength N − H···O hydrogen bond and a supplementary weak stabilized H…F hydrogen bonds.

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Data availability

The data that support the findings of this study are available in the supplementary material of this article.

Code availability

All calculations have been performed using the Gaussian 09 program and Multiwfn.

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Funding

This work was supported by the Ministry of Higher Education and Scientific Research of the Algerian Government [project PRFU Code: A6N0UN202090005].

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Authors and Affiliations

  1. Laboratory of Materials and Energetic Engineering, Faculty of Technology, University 20 August 1955 Skikda, BP 26, 21000, Skikda, Algeria

    Hanifa Chouit, Chafia Sobhi, Souad Bouasla, Samia Messikh & Azeddine Kheribeche

  2. Department of Physics and Chemistry, Higher Normal School for Technological Education of Skikda, Azzaba, Skikda, Algeria

    Souad Bouasla

  3. Laboratory of Physical Chemistry and Biology of Materials, Department of Physics and Chemistry, Higher Normal School for Technological Education of Skikda, Azzaba, Skikda, Algeria

    Abdelmalek Khorief Nacereddine

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  1. Hanifa Chouit
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Contributions

Computational calculations were performed by Miss. Hanifa Chouit, conceptualization, methodology and writing original draft of the article were done by Dr. Chafia Sobhi, data curation was done by Dr. Bouasla Souad, the visualization was performed by Miss. Samia Messikh, formal analysis was done by Mr. Azeddine Kheribeche, and reviewing of the article draft and submitting the article were performed by Prof. Abdelmalek Khorief Nacereddine.

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Correspondence to Chafia Sobhi or Abdelmalek Khorief Nacereddine.

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Chouit, H., Sobhi, C., Bouasla, S. et al. Effect of hydrogen bonds and CF3 group on the regioselectivity and mechanism of [3 + 2] cycloaddition reactions between nitrile oxide and 2,4-disubstituted cyclopentenes. A MEDT study. J Mol Model 28, 104 (2022). https://doi.org/10.1007/s00894-022-05086-y

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