Pd-catalyzed γ-arylation of γ,δ-unsaturated O-carbamates via an unusual haptotropic rearrangement

Abstract

An unusual γ-selectivity was observed in the arylation of γ,δ-unsaturated O-carbamates involving directed lithiation, transmetallation to zinc and Negishi coupling, when a specific combination of aryl electrophile and phosphine ligand is employed. Mechanistic studies indicate that an unusual, stereospecific haptotropic rearrangement of the palladium-diene intermediate is involved.