Theoretical Study of Electroreductive Intramolecular Coupling of Nonconjugated Olefinic and Aromatic Ketones

The electroreductive cyclization of hept-6-en-2-one, octa-7-en-2-one, and 5-phenylpentan-2-one was
investigated by ab initio (UHF/6-311++G**) and density functional (UB3LYP/6-311++G**)
calculation methods. The high regio- and stereoselectivities previously reported for olefinic ketones
(exo-trans) and 5-arylpentan-2-ones (endo-trans) were reconfirmed. These experimental results well
agree with the computational outcome for the transition states in the intramolecular coupling of
ketyl radicals generated by one-electron transfer to the ketones.