Alkylation of Allylic Derivatives. 14. Relationship of Double-Bond Configuration between Reactant and Product for Cross-Coupling Reactions of Z-Allylic Carboxylates with Organocopper Reagents

Article abstract of DOI:10.1021/jo00271a024

Cross-coupling reactions of alkylcuprates (sp³ reagents) with allylic carboxylates can result in loss of double-bond configuration in the α-alkylation product.Loss of configuration occurs during the reaction, which shows that an intermediate is involved in which the double bond is temporarily relocated.With phenyl- and vinylcuprates (sp² reagents) the original double-bond configuration is fully preserved in all cases.This shows that the original double bond is partly retained throughout the reaction.Evidently with sp² reagents, oxidative addition leads directly to a ?-allylcopper(III) complex (12).