Allylic Aminations with Hindered Secondary Amine Nucleophiles Catalyzed by Heterobimetallic Pd–Ti Complexes

Phosphinoamide-scaffolded
heterobimetallic palladium–titanium
complexes are highly effective catalysts for allylic aminations of
allylic chlorides with hindered secondary amine nucleophiles. Three
titanium-containing ligands are shown to assemble active catalysts in situ and enable catalysis at room temperature. A variety
of sterically bulky secondary amines are efficiently allylated in
high yields with as little as 1 mol % palladium catalyst. Piperidine
and pyrrolidine products are also efficiently generated via intramolecular
aminations with hindered amine nucleophiles.