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.
Kise
Naoki
N
Department of Biotechnology, Faculty of Engineering, Tottori University, Koyama, Tottori 680-8552, Japan. kise@bio.tottori-u.ac.jp