Synthesis of Homoallylamines Enabled by Cobalt or Palladium Catalyzed Allylic Substitution of Azaarylmethylamines.

Pd(OAc) 2 /Nixantphos or CoI 2 /Nixantphos catalyzed allylic substitutions with weakly acidic C(sp) 3 -H bonds of azaarylmethylamines are described. This method facilitates access to various kinds of heteroaryl rings containing homoallylamines (39 examples, 30-98% yields) with excellent functional group tolerance and diastereoselectivity. Compared with the Pd/Nixantphos complex, the Co/Nixantphos catalysis could obtain the cyclic products with good to excellent diastereoselectivities. Importantly, the CoI 2 /( R,R )-Me-Duphos catalyzed reactions exhibit moderate enantioselectivity. Additionally, the scalability of this transformation is successfully demonstrated.