The direct functionalization of C(sp3)–H and C(sp3)–C(sp3) bonds is considered as one of the most valuable synthetic strategies because of its high efficiency and step-economy for the rapid assembly of complex molecules. However, the relatively high bond disassociation energies (BDEs) and similar chemical environment lead to large obstacles in terms of low reactivity and selectivity. Using a radical-based strategy has proved to be an efficient approach to overcome these difficulties via a hydrogen atom transfer (HAT) process for selective C(sp3)–H functionalization and β-carbon scission for C(sp3)–C(sp3) bond derivatization. Oxime esters have emerged as outstanding precursors of iminyl radicals for versatile chemical transformations. This short review summaries the recent advances in site-specific C(sp3)–H functionalization and C(sp3)–C(sp3) bond cleavage starting from oxime esters by our group and pioneering work by others, mainly focusing on the reaction design as well as the reaction mechanism.1 Introduction2 C(sp3)–H Bond Functionalization via 1,5-HAT of Acyclic Oxime Esters­2.1 1,5-HAT/Cyclization2.2 1,5-HAT/C–C or C–Heteroatom Bond Formation3 C(sp3)–C(sp3) Bond Functionalization via β-Carbon Scission of Cyclic Oxime Esters3.1 β-Carbon Scission/C–C or C–Heteroatom Bond Formation3.2 β-Carbon Scission/Cyclization4 Conclusion and Outlook

中文翻译：

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通过 1,5-HAT 和 β-碳断裂对肟酯进行亚胺基触发 C-H 和 C-C 键官能化的最新进展

C(sp3)-H 和 C(sp3)-C(sp3) 键的直接功能化被认为是最有价值的合成策略之一，因为它具有快速组装复杂分子的高效率和分步经济性。然而，相对较高的键解离能 (BDE) 和类似的化学环境导致在低反应性和选择性方面存在很大障碍。使用基于自由基的策略已被证明是克服这些困难的有效方法，通过氢原子转移 (HAT) 过程进行选择性 C(sp3)–H 官能化和 C(sp3)–C(sp3) 的 β-碳断裂键衍生。肟酯已成为用于多种化学转化的亚胺基自由基的杰出前体。