Aliphatic amines are pivotal organic molecules, and therefore the precise C—H transformation of amines at distinct sites has long been a research focus in organic synthesis. Hydrogen atom transfer (HAT), recognized as a mild and controllable strategy for C—H activation, has attracted considerable attention in recent years and is extensively employed for the selective C—H transformation of amine molecules. By leveraging intermolecular or intramolecular HAT processes, it becomes feasible to precisely abstract C—H bonds at specific sites within amine molecules and facilitate subsequent transformations, providing novel synthetic pathways for the efficient construction of complex functional amine molecules. The recent advances in the selective functionalization of C—H bonds of amine molecules using the aforementioned strategy are comprehensively summarized. A review is conducted on the regio-, chemo-, and stereoselective regulatory mechanisms, as well as the reaction mechanisms involved. In addition, the limitation in this research field is analyzed and the outlook of this area is also prospected.

Key words: hydrogen atom transfer, amine, C—H functionalization, regioselectivity, stereoselectivity, radical