Chem ( IF 23.5 ) Pub Date : 2022-05-13 , DOI: 10.1016/j.chempr.2022.04.018 Bijin Li , Mazen Elsaid , Haibo Ge
C(sp3)–H bonds are ubiquitously present in natural raw materials. Direct functionalization of these bonds provides a highly valuable approach to increasing molecular complexity. However, the inertness of these bonds and their high bond-dissociation energies, low acidity, and unreactive molecular orbital profiles make them challenging reaction components. To overcome these hurdles, the site-selective C(sp3)–H functionalization approach has been developed via various strategies that provide distinct, straightforward, and atom-efficient access to constructing C–C and C–X bonds. This review discusses transition-metal-catalyzed site-selective γ- and δ-C(sp3)–H functionalization of simple aliphatic substrates. The purpose of this review is to characterize the current state of the art in transition-metal-catalyzed site-selective γ- and δ-C(sp3)–H functionalization reactions, their mechanisms, and their application in the late-stage functionalization of medicinal compounds and the construction of medicinally important complex molecules.
中文翻译:
过渡金属催化的位点选择性 γ- 和 δ-C(sp3)-H 官能化反应
C(sp 3 )-H 键普遍存在于天然原料中。这些键的直接功能化为增加分子复杂性提供了一种非常有价值的方法。然而,这些键的惰性及其高键解离能、低酸度和非反应性分子轨道分布使它们具有挑战性的反应组分。为了克服这些障碍,已经通过各种策略开发了位点选择性 C(sp 3 )-H 官能化方法,这些策略提供了独特、直接和原子高效的构建 C-C 和 C-X 键的途径。本综述讨论了过渡金属催化的位点选择性 γ- 和 δ-C(sp 3)–H 功能化简单的脂肪族底物。本综述的目的是描述过渡金属催化的位点选择性 γ- 和 δ-C(sp 3 )-H 官能化反应的现有技术、它们的机制以及它们在后期官能化中的应用药用化合物的合成和医学上重要的复杂分子的构建。