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

Pd(OAc)2/Nixantphos or CoI2/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 CoI2/(R,R)-Me-Duphos catalyzed reactions exhibit moderate enantioselectivity. Additionally, the scalability of this transformation is successfully demonstrated.