C–H bond functionalization represents one of the most efficient and straightforward strategies for diversifying existing molecules. The most challenging task to achieve is the site-selective C(sp³)–H functionalization of primary aliphatic amines in modern organic synthesis, which has received much attention in recent years. On the one hand, the combining of 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 also been made in native amine-directed γ- and δ-C(sp³)–H functionalization catalyzed by palladium catalysts. In this review, we systematically summarize the site-selective C(sp³)–H functionalization of primary aliphatic amines, as well as discuss the mechanisms.

中文翻译：

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脂肪伯胺的位点选择性 C(sp3)–H 官能化

C-H 键功能化代表了现有分子多样化的最有效和最直接的策略之一。现代有机合成中最具挑战性的任务是脂肪族伯胺的位点选择性C(sp ³ )–H官能化，近年来备受关注。一方面，通过自由基途径实现了光氧化还原催化（PC）和氢原子转移（HAT）相结合的α-C(sp ³ )–H功能化。另一方面，钯催化剂催化的天然胺导向的γ-和δ-C(sp ³ )-H官能化也取得了重大进展。在这篇综述中，我们系统地总结了脂肪伯胺的位点选择性C(sp ³ )–H官能化，并讨论了其机制。