Anti-Markov­nikov Hydroamination of Homoallylic Amines

The development of an anti-Markov­nikov-selective hydro­amin­ation of unactivated alkenes is a significant challenge in organo­metallic chemistry. Herein, we present the rhodium-catalyzed anti-Markov­nikov-selective hydro­amin­ation of homoallylic amines. The proximal Lewis basic amine serves to promote reactivity and enforce regio­selectivity through the formation of the favored metallacycle, thus over-riding the inherent reactivity of the alkene. The scope of both the amine nucleo­philes and homoallylic amines that participate in the reaction is demonstrated.