γ,γ′-Diarylation of allylamines by a directed chain-walk

Directed chain-walking is an important organometallic methodology that can be used to functionalize C–H bonds by metal movement along the hydrocarbon chain of a substrate, giving rise to difunctionalized products. We have demonstrated that using trifluoroacetic acid (TFA) as a co-solvent we can achieve directed chain-walking on free amines without concomitant oxidation of the product. The reaction proceeds through an amine-directed γ-insertion of arene, kinetically-driven β-hydride elimination, and then γ′-insertion.