stereochemistry of the epoxidation of bicyclo[2.2.1]hept-2-ene and its 7-syn-substituted derivatives. a dft study

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ID: 214387
2014
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Abstract
The stereochemical aspects of epoxidation of norbornene and its 7-syn-substituted derivatives by performic acid were investigated. Geometry and thermodynamic parameters of transition states and prereactive complexes were computed at the UBHandHLYP/6-31G(d) level of theory. It is shown that the transition states have a pronounced biradical character and a nearly coplanar orientation of the C=C bond and the molecule of performic acid. Transition state analysis revealed that, in the case of the syn-7-hydroxy derivative, the preference for the exo-approach of the oxidant can be explained by the stabilization of transition state with hydrogen bonding. In contrast, a chlorine atom or a methyl group at the 7-syn position facilitated the formation of endo-epoxides due to steric repulsion between the substituent and the oxidant.
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okovytyy2014vsnikstereochemistry Use this key to autocite in the manuscript while using SciMatic Manuscript Manager or Thesis Manager
Authors ;Sergiy I. Okovytyy;Oleksandr A. Zhurakovskyi
Journal applied and environmental soil science
Year 2014
DOI
10.15421/081409
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