Recent advances in copper-catalyzed direct hydroamination of alkenes with (hetero)aromatic amines.

Nitrogen-containing aromatic amines and aza-heterocycles are ubiquitous motifs in pharmaceuticals and functional materials, making efficient C-N bond formation a fundamental transformation in synthetic chemistry. The direct hydroamination of alkenes using (hetero)aromatic N-H nucleophiles offers an atom- and step-economical strategy; however, the reduced nucleophilicity and distinct coordination behavior of these substrates render such transformations inherently challenging. Recently, copper catalysis has emerged as a versatile and practical platform for addressing these limitations. Owing to its redox flexibility and ligand tunability, copper facilitates multiple activation modes, including copper-amido-mediated nucleophilic addition or aminocupration, Lewis acid-type alkene activation, and radical-mediated pathways. These complementary mechanisms provide access to diverse alkene classes with control over regioselectivity (Markovnikov vs anti-Markovnikov addition), stereoselectivity, and functional group tolerance. This review summarizes recent advances in the copper-catalyzed hydroamination of alkenes with (hetero)aromatic N-H nucleophiles, emphasizing the mechanistic paradigms and the factors governing selectivity.