Asymmetric Hydroamination From Metal Catalysis to Metal‐Free and Biocatalytic Approaches

ABSTRACT Asymmetric hydroamination is a key transformational method in contemporary synthetic chemistry, crucial for constructing chiral nitrogen‐containing compounds that are widely found in pharmaceuticals and functional materials, with its advantages lying in its excellent atom economy. This reaction directly couples alkenes, dienes, or alkynes with various amines to achieve asymmetric C─N bond formation in one step, offering a straightforward and precise route for synthesizing complex chiral amines, alkaloids, and key nitrogen heterocycles like pyrrolidines and piperidines. In this review, the research progress of asymmetric hydroamination is systematically summarized, focusing on the catalytic system and reaction mechanism. It covers the evolution of catalytic systems from early transition metals and platinum group metals to the first‐row transition metals (such as Cu, Co, Ni, Mn), and extends to metal‐free organic catalysis and emerging enzyme catalytic strategies. At the same time, the key mechanism models of classical direct N─H addition, formal hydroamination and Cope‐type hydroamination were compared and discussed. It aims to provide a clear reference framework for the future development of this field.