Lakshminarayanan Akilandeswari
Articles written in Journal of Chemical Sciences
Volume 121 Issue 5 September 2009 pp 859-866
Fluorine effect on pericyclic and pseudopericyclic processes: Evidences and
Lakshminarayanan Akilandeswari Madhavan Jaccob Ponnambalam Venuvanalingam
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.
Volume 127 Issue 9 September 2015 pp 1505-1511
Lakshminarayanan Akilandeswari Chandrasekaran Prathipa
The competition between the two electron donors (–OCH3 and –OSiH3) have been studied by positioning them at
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