Anti-Markovnikov Hydroamination of Homoallylic Amines

• DOI: 10.1021/jacs.5b08500
• Publication Date: 2015-10-12T12:00:10Z
• Authors: Seth C. Ensign; Evan P. Vanable; Gregory D. Kortman; Lee J. Weir; Kami L. Hull
• Keywords: 01 natural sciences; 0104 chemical sciences

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.