Anti-Markovnikov hydroamination

Organic Chemistry Catalytic hydroamination is an efficient and waste-free way to form amines, enamines, and imines, which are important synthetic intermediates in many organic syntheses of bioactive compounds and often have essential physiological and biological activity themselves. The development of these types of hydroamination reactions is a persistent research topic in organic and pharmaceutical chemistry. Miller et al. report a synthetic protocol for the intermolecular anti-Markovnikov hydroamination of unactivated alkenes with primary alkylamines to generate secondary amine products in the presence of an iridium photocatalyst and a thiol cocatalyst. This protocol addresses a long-standing synthetic challenge of monoalkylation of primary amines and demonstrates high selectivity for secondary amines over tertiary amine products, though further work is required to understand its underlying mechanism. J. Am. Chem. Soc. 141 , 16590 (2019).