The C-H bond functionalization represents one of the most efficient and straightforward strategies to diversify the existing molecules. It is the most challenging task to achieve the site-selective C(sp3)-H functionalization of unprotected primary aliphatic amines in organic synthesis, which has received increasing attention in the recent years. On the one hand, the combining photoredox catalysis (PC) and hydrogen atom transfer (HAT) for α-C(sp3)-H functionalization has been achieved via a free radical pathway. On the other hand, significant progress has been made in native directed γ- and δ-C(sp3)-H functionalization catalyzed by palladium catalysts. In this review, we systematically summarized the site-selective C(sp3)-H functionalization of unprotected primary aliphatic amines, and their mechanisms were also discussed.

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