Collect. Czech. Chem. Commun.
2011, 76, 947-956
https://doi.org/10.1135/cccc2011042
Published online 2011-07-07 13:15:49
Intramolecular addition of oxyradicals to benzene rings: A DFT study
Götz Bucher
WestCHEM, School of Chemistry, University of Glasgow, Joseph-Black-Building, Glasgow G12 8QQ, UK
Abstract
The reactivity of a series of oxyradicals related to the triplet state of β-phenylpropiophenone was investigated by density functional theory. Analysis of the potential energy hypersurfaces indicates that radical addition to the β-phenyl ring should occur with a smaller barrier than intramolecular hydrogen abstraction from the benzylic position, although the latter reaction is far more exothermic. Addition can occur in ipso- and ortho-position of the β-phenyl ring, with ortho addition being slightly more favourable. As both addition reactions are predicted to be mildly exothermic and exergonic, intermolecular trapping of the resulting cyclohexadienyl- type radicals should be feasible.
Keywords: Ab initio calculations; Density functional calculations; Radical reactions; Cyclization.
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