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A conceptual DFT analysis of the plausible mechanism of some pericyclic reactions

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Abstract

Out of several pericyclic reactions, Diels-Alder (DA) reaction is one of the most widely used synthetic processes. In the present work, several models and methodologies have been used to determine and to analyze the plausible mechanism of some representative DA cycloaddition reactions. A comparison between the dual descriptor and the bond reactivity indices corresponding to the natural bond orbital of the reagents is included, which provides a complete description of the plausible reaction mechanism. In the next step, two very recent models are used to determine the local electronic density transfer and redistribution between the reactants involved. The description of the local electronic density transfer has been made in two stages; first, the variation in the net charge on the atoms is obtained, and then, the electronic density transfer between the natural bond orbitals is calculated. The values obtained using the two models are correlated with the experimental rate constants of the reactions. Finally, the natural bond orbitals are obtained at several steps along the reaction path and the variation in their partial occupation is compared with the corresponding electron density transfer among these orbitals. Furthermore, frontier molecular orbital (FMO) approach has been employed to understand the more feasible way of interaction between the DA pair. Relative electrophilicity descriptors like net electrophilicity (∆ω±), net reactivity index (NRI, Δ\( {\omega}_R^{\pm } \)), and electrophilicity difference (∆ω) between DA pairs have also been employed to describe the studied reaction mechanisms especially whether they follow non-polar-concerted/polar-stepwise pathway along with their classification in terms of normal or inverse electron demand. Furthermore, adaptive natural density partitioning method (AdNDP) and energy decomposition analyses (EDA) in conjunction with natural orbital for chemical valence (NOCV) have been made use of in order to analyze the actual bonding situation in the transition state (TS).

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Acknowledgments

PKC thanks the DST, New Delhi, for the J. C. Bose National Fellowship. AM thanks the GIBACUS (Universidad del Sinú, sectional Cartagena), and JS thanks the Departamento de Química-Física for the support of this investigation. GJ thanks IIT, Kharagpur for his fellowship.

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Authors and Affiliations

  1. Grupo de Investigaciones Básicas y Clínicas de la Universidad del Sinú (GIBACUS), escuela de medicina, Universidad del Sinú, Cartagena, Colombia

    Alejandro Morales-Bayuelo

  2. Departamento de Química-Física, Facultad de Ciencias, Campus Universitario Río San Pedro, Universidad de Cádiz, Cádiz, Spain

    Jesús Sánchez-Márquez

  3. Department of Chemistry and Center for Theoretical Studies, Indian Institute of Technology Kharagpur, Kharagpur, 721302, India

    Gourhari Jana & Pratim Kumar Chattaraj

  4. Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India

    Pratim Kumar Chattaraj

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  1. Alejandro Morales-Bayuelo
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  3. Gourhari Jana
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  4. Pratim Kumar Chattaraj
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Correspondence to Alejandro Morales-Bayuelo or Pratim Kumar Chattaraj.

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Morales-Bayuelo, A., Sánchez-Márquez, J., Jana, G. et al. A conceptual DFT analysis of the plausible mechanism of some pericyclic reactions. Struct Chem 31, 1745–1756 (2020). https://doi.org/10.1007/s11224-020-01527-7

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