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Density functional theory study of the regio‐ and stereoselectivity of 1,3-dipolar cycloaddition reactions between 2-ethylthio-4-phenyl-1-azetin and some substituted nitrile oxides

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Abstract

The mechanism (regio- and stereoselectivity) of 1,3-dipolar cycloaddition (1,3-DC) of 2-ethylthio-4-phenyl-1-azetin 1 with benzonitrile oxide 2a, 2-aminobenzonitrile oxide 2b and 2-azidobenzonitrile oxide 2c has been investigated by density functional theory-based reactivity indices and activation energy calculations at B3LYP/6-31G(d,p) level of theory in the gas and solvent phase. Thermodynamic and kinetic parameters of the possible ortho/meta regioisomeric and endo/exo stereoisomeric pathways have been determined. In order to rationalize complete endo selective fashion provided by these 1,3-DC cycloadditions, a natural steric analysis between NLMOs i,j for TS1ox and TS1on and also a second-order interaction energy, E 2, analysis between the donor–acceptor orbitals in these TSs were carried out. In all cases, the ortho pathways are more favorable compared to the meta alternatives and it is found that the endo pathway is preferred. Our results show that these cycloadditions follow an asynchronous one-step mechanism with a nonpolar character. Theoretical data are in good agreement with the experimental results.

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Acknowledgments

The financial support for this work was provided by Research Council of Ferdowsi University of Mashhad (Grant No. 3/29765) and Islamic Azad University, Bandar Abbas Branch.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran

    Amir Khojastehnezhad, Hossein Eshghi, Mehdi Bakavoli, Mohammad Izadyar & Javad Tajabadi

  2. Department of Chemistry, Faculty of Sciences, Bandar Abbas Branch, Islamic Azad University, Bandar Abbas, 7915893144, Iran

    Farid Moeinpour

Authors
  1. Amir Khojastehnezhad
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  2. Hossein Eshghi
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  3. Farid Moeinpour
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  4. Mehdi Bakavoli
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  5. Mohammad Izadyar
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  6. Javad Tajabadi
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Corresponding authors

Correspondence to Hossein Eshghi or Farid Moeinpour.

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Khojastehnezhad, A., Eshghi, H., Moeinpour, F. et al. Density functional theory study of the regio‐ and stereoselectivity of 1,3-dipolar cycloaddition reactions between 2-ethylthio-4-phenyl-1-azetin and some substituted nitrile oxides. Struct Chem 27, 1041–1047 (2016). https://doi.org/10.1007/s11224-015-0703-8

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  • DOI: https://doi.org/10.1007/s11224-015-0703-8

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