REACTIVITE DES β-CYCLOPROPYL α-ENONES--I. ETUDE DES TRANSFERTS ELECTRONIQUES PAR VOLTAMETRIE CYCLIQUE ET DE LA REDUCTION PAR L'ELECTRON SOLVATE DANS L'AMMONIAC LIQUIDE

Article abstract of DOI:10.1016/S0040-4020(01)98848-9

Species produced by electron transfer to variously substituted bicyclo<3.1.0>hex-3-en-2-ones provide a better insight into the origin of 1,6-addition products sometimes observed by reaction of lithium diorganocuprates with β-cyclopropyl α-enones.Cyclic voltammetry of eight such bicyclohexenones show that the half-lives of the corresponding anion radicals are very short (t_1/2=<10 E-4s) except when the initial molecule is phenyl substituted at C-4.In such cases the anion radicals are very stable (t_1/2=>6s) owing to the greater charge delocalization and we observe a second wave corresponding to the formation of the dianion.The reduction of the same substrates by the solvated electron in liquid ammonia exhibits the same difference of behaviour.The molecules giving strongly reactive anion radicals only lead to the straight-forward product expected by conjugate reduction; while the 4-phenyl substituted substrates yield a mixture of products from normal conjugate reduction and rearrangement.This correlation strongly suggest that these last products arise from the rearrangement of the dianion.