Silver-Free Palladium-Catalyzed C(sp 3 )-H Arylation of Saturated Bicyclic Amine Scaffolds.

Herein, we report a silver-free Pd(II)-catalyzed C(sp3 )-H arylation of saturated bicyclic and tricyclic amine scaffolds. The reaction provides good yields using a range of aryl iodides and aryl bromides including functionalized examples bearing aldehydes, ketones, esters, free phenols, and heterocycles. The methodology has been applied to medicinally relevant scaffolds. Two of the intermediate palladium complexes in the catalytic cycle have been prepared and characterized, and a mechanism is proposed. Removal of the directing group proceeded with good yield under relatively mild conditions.