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Unveiling the mechanism and selectivity of [3+2] cycloaddition reactions of benzonitrile oxide to ethyl trans-cinnamate, ethyl crotonate and trans-2-penten-1-ol through DFT analysis

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Abstract

The mechanism and regioselectivity of [3+2] cycloaddition (32CA) reactions of benzonitrile oxide with ethyl trans-cinnamate, ethyl crotonate and trans-2-penten-1-ol has been studied in gas phase and in acetonitrile, ethyl acetate and tetrahydrofuran using the B3LYP functional in connection with 6-31G(d) basis set. The 32CA reactions followed one-step mechanism with asynchronous TSs. The calculated global electron density transfer (GEDT) at the TSs showed electronic flux from benzonitrile oxide to ethyl trans-cinnamate and ethyl crotonate, while the electronic flux from trans-2-penten-1-ol to benzonitrile oxide was predicted, in complete agreement with the Conceptual Density Functional Theory (CDFT) indices. The regioselectivity is correctly described in coherence with the experiment data. The intermolecular interaction at the TSs was realized through visualization and quantification by means of independent gradient model (IGM) analysis based on promolecular density.

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Authors and Affiliations

  1. Applied Chemistry-Physics and Environment Team, Faculty of Sciences, Ibn Zohr University, B. P. 8106 Cité Dakhla, Agadir, Morocco

    Khalid Abbiche & Mustapha Hilali

  2. Polydisciplinary Faculty of Taroudant, Ibn Zohr University, Hay El Mohammadi (Lastah), BP. 271, 83000, Taroudant, Morocco

    Khalid Abbiche & Abdelatif Laknifli

  3. Department of Chemistry, Durgapur Government College, Durgapur, Paschim Bardhaman, West Bengal, 713214, India

    Nivedita Acharjee

  4. Molecular Modeling and Spectroscopy Research Team, Department of Chemistry, Faculty of Science, Chouaïb Doukkali University, P. O. Box 20, 24000, El Jadida, Morocco

    Mohammed Salah

  5. Laboratory of Spectroscopy, Molecular Modeling, Materials, Nanomaterials, Water and Environment, Department of Chemistry, Faculty of Sciences, University Mohammed V, Avenue Ibn Battouta, B. P 1014, Rabat, Morocco

    Najia Komiha & Khadija Marakchi

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  1. Khalid Abbiche
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Tables with total energies, enthalpies, free energies and entropies and tables with calculated bond lengths and bond angles of the stationary points optimized along the 32CA reaction of BNO with 1b, 2b and 3b. (DOCX 3482 kb)

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Abbiche, K., Acharjee, N., Salah, M. et al. Unveiling the mechanism and selectivity of [3+2] cycloaddition reactions of benzonitrile oxide to ethyl trans-cinnamate, ethyl crotonate and trans-2-penten-1-ol through DFT analysis. J Mol Model 26, 279 (2020). https://doi.org/10.1007/s00894-020-04547-6

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