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      https://www.ias.ac.in/article/fulltext/jcsc/121/05/0859-0866

    • Keywords

       

      Pericyclic reaction; pseudeopericyclic reaction; fluorine; NICS(0); orbital disconnections; NBO analysis.

    • Abstract

       

      Electrocyclic ring opening (ERO) reactions of 2-pyrone, 2-pyranol and pyran and their fluoro compounds (1-6) have been studied at MP2/6-31G(𝑑) level with special emphasis on the influence of fluorine on these pericyclic/pseudopericyclic processes. Calculations clearly predict that substitution of fluorine at C6 favour the reaction both kinetically and thermodynamically. Magnetic susceptibility anisotropy ($\Delta_{\chi\text{aniso}}$), NICS(0), NBO and bond critical property (BCP) analyses clearly illustrate the following; 2-pyrone (1) and 6-fluoro-2-pyrone (2) reactions are pseudopericyclic; 6-fluoro-2-pyranol (reaction 4) corresponds to a borderline case; 2-pyranol (3) and pyran (5) and 6-fluoro pyran (6) reactions are clearly pericyclic in character. Correspondingly pseudeopericyclic reactions show up orbital disconnections and fluorine delays the occurrence of orbital disconnections on the reaction trajectory.

    • Author Affiliations

       

      Lakshminarayanan Akilandeswari1 2 Madhavan Jaccob1 Ponnambalam Venuvanalingam1

      1. School of Chemistry, Bharathidasan University, Tiruchirapalli 620 024
      2. Department of Chemistry, Sri Sarada College for Women, Salem 636 016
    • Dates

       
  • Journal of Chemical Sciences | News

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