Intra- and Intermolecular Anti-Markovnikov Hydroamination of Unactivated Olefins with Alkylamines

Abstract

While the addition of N-H bonds across an olefin represents a green and direct method for the formation of amine products central to many branches of academic research and industry, catalytic hydroaminations with anti-Markovnikov selectivity remain rare. Based on a classical olefin amination reaction that proceeds through an aminium radical cation, herein we report protocols for both an intra- and intermolecular anti-Markovnikov hydroamination of unactivated olefins with simple alkylamines using an iridium visible-light photocatalyst in conjunction with an H-atom donor. A range of alkyl amines, including β-aminoalcohols, have been prepared under these mild catalytic conditions in good to excellent yields.