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A molecular electron density theory study to understand the interplay of theory and experiment in nitrone-enone cycloaddition

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Abstract

[3 + 2] cycloaddition (32CA) reaction of C,N-diaryl nitrone with benzylidene acetone has been studied to analyse the mechanism, selectivity and polar character of this nitrone-enone cycloaddition. Topological analysis of the electron localization function (ELF) shows the absence of pseudoradical and carbenoid centre in the nitrone, which allows its classification as a zwitter-ionic (zw) type three atom component (TAC) and hence participation in zw- type cycloadditions is associated with high activation energy barriers. This 32CA reaction follows a one-step mechanism with asynchronous TSs. Endo/meta product is obtained as the major cycloadduct experimentally, which can be rationalized from its calculated lowest activation energy among the four possible reaction pathways. Global electron density transfer (GEDT) at the TSs predict the non-polar character of this 32CA reaction. Topological analysis of the ELF and QTAIM parameters was performed at the TSs. Finally, non-covalent interaction (NCI) gradient isosurfaces are computed to obtain a visualization of non-covalent interactions at the interatomic bonding regions.

Graphic Abstract

The experimental and theoretical aspects of [3+2] cycloaddition reactions of C,N-diaryl nitrone with benzylidene acetone is described. The reaction is meta/endo selective and follows one step mechanism with non-covalent interactions. The C-C and C-O bonds are generated through coupling of pseudoradical centers.

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Acknowledgements

One of the authors N. Acharjee, is thankful to Professor Manas Banerjee (Retired), University of Burdwan, West Bengal, India for kind cooperation and University of Calcutta for experimental facilities.

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Authors and Affiliations

  1. Department of Chemistry, Durgapur Government College, Durgapur, West Bengal, 713214, India

    NIVEDITA ACHARJEE

  2. Department of Chemistry, National Institute of Ayurvedic Drug Development, Salt Lake, Kolkata, West Bengal, India

    AVIJIT BANERJI

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Correspondence to NIVEDITA ACHARJEE.

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ACHARJEE, N., BANERJI, A. A molecular electron density theory study to understand the interplay of theory and experiment in nitrone-enone cycloaddition. J Chem Sci 132, 65 (2020). https://doi.org/10.1007/s12039-020-01766-5

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