Direct Insertion of Aluminum to Functionalized Unsaturated Halides

Significance

In the presence of catalytic amounts of selected metallic chlorides (TiCl₄, BiCl₃, InCl₃, PbCl₂) as well as LiCl, aluminum powder is shown to insert into various unsaturated iodides and bromides under mild conditions. The resulting organoaluminum reagents readily undergo palladium-catalyzed cross-coupling, acylation or copper-catalyzed allylic substitution, giving rise to functionalized biaryls, diaryl ketones or allyl arenes in high yields.