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

Abstract

Ortho-amino arenethiolatocopper(I) compounds are excellent catalysts for the cross-coupling reaction of Grignard reagents with acyclic allylic substrates. For example, reaction of n-BuMgI with geranyl acetate in Et{2}O at 0 }o{C yields quantitatively the @c substitution product, whereas the same reaction in THF at -30 }o{C affords selectively the @a substitution product.