Anti-Markovnikov Hydroamination of Homoallylic Amines

http://pubs.acs.org/doi/abs/10.1021/jacs.5b08500

Seth C. Ensign, Evan P. Vanable, Gregory D. Kortman, Lee J. Weir, and Kami L. Hull*

Department of Chemistry, University of Illinois at Urbana−Champaign, 600 South Mathews Avenue, Urbana, Illinois 61820, United States

J. Am. Chem. Soc., Article ASAP

DOI: 10.1021/jacs.5b08500

Publication Date (Web): October 12, 2015

Copyright © 2015 American Chemical Society

Abstract: 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.