The Use of Ortho-Chelating Arenethiolate Non-transferable Groups in the Copper(I) Catalyzed Selective α or γ Substitution of Acyclic Allylic Substrates with Grignard Reagents

Article abstract of DOI:10.1016/S0040-4039(00)78222-0

Ortho-amino arenethiolatocopper(I) compounds are excellent catalysts for the cross-coupling reaction of Grignard reagents with acylic allylic substrates.For example, reaction of n-BuMgI with geranyl acetate in Et2O at 0 deg C yields quantitatively the γ substitution product, whereas the same reaction in THF at -30 deg C affords selectively the α substitution product.