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Unveiling the synthesis of spirocyclic, tricyclic, and bicyclic triazolooxazines from intramolecular [3 + 2] azide-alkyne cycloadditions with a molecular electron density theory perspective

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Abstract

The intramolecular [3+2] cycloaddition (32CA) reactions of azido alkynes leading to spirocyclic, tricyclic, and bicyclic triazolooxazines has been studied within the molecular electron density theory (MEDT) at the MPWB1K/6-311G(d,p) level. The electron localization function (ELF) characterizes the azido alkynes as zwitterionic species. Analysis of the conceptual DFT indices allows classifying the azide moiety as the electrophilic counterpart and the alkyne as the nucleophilic one. These 32CA reactions are under kinetic control with the activation free energies of 23.4–26.7 kcal mol−1. Along the reaction path, the pseudoradical centre is created initially at C4, consistent with the Parr function analysis; however, the sequence of bond formation is controlled by the energetically feasible formation of the six-membered oxazine ring. The intermolecular interactions at the transition states were characterized from the quantum theory of atoms in molecules (QTAIM) study and the non-covalent interaction (NCI) gradient isosurfaces.

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All datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

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Authors and Affiliations

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

    Nivedita Acharjee

  2. Department of Chemistry, University of Zakho, Duhok, 42001, Iraq

    Haydar A Mohammad-Salim

  3. Department of Electronics and Communication Engineering, Dr. B. C. Roy Engineering College, Durgapur, 713206, West Bengal, India

    Mrinmoy Chakraborty

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  1. Nivedita Acharjee
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  2. Haydar A Mohammad-Salim
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  3. Mrinmoy Chakraborty
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All authors contributed to the study conception and design. Data collection and analysis were performed by Nivedita Acharjee, Haydar A Mohammad-Salim, and Mrinmoy Chakraborty. The first draft of the manuscript was written by Nivedita Acharjee, and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Nivedita Acharjee.

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Acharjee, N., Mohammad-Salim, H.A. & Chakraborty, M. Unveiling the synthesis of spirocyclic, tricyclic, and bicyclic triazolooxazines from intramolecular [3 + 2] azide-alkyne cycloadditions with a molecular electron density theory perspective. Struct Chem 33, 555–570 (2022). https://doi.org/10.1007/s11224-021-01870-3

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