Abstract Intermolecular C(sp 3)–H bond functionalization reactions promise to revolutionize how we synthesize organic molecules by enabling the introduction of functionality at previously inert sites. However, one of the greatest challenges in this research field is site-selectivity, wherein chosen C(sp 3)–H bonds must be selectively functionalized and other C(sp 3)–H bonds with similar stereoelectronic properties must remain intact. To address this problem, chemists have developed methods that rely on targeting innately more reactive C(sp 3)–H bonds or on using pre-installed functional groups to direct a catalyst or reagent to a particular C(sp 3)–H bond. However, such approaches invariably have limited applicability because only a handful of innately reactive C(sp 3)–H bonds or those nearby certain functional groups can be functionalized with good site-selectivity. To overcome these limitations, chemists also have developed catalysts and reagents that control the site of C(sp 3)–H bond functionalization and have begun to unlock the potential of these reactions to achieve the site-divergent functionalization of C(sp 3)–H bonds, wherein the site of functionalization is changed by modulating the stereoelectronic properties of the catalyst or reagent. This short review will provide a summary of selected examples of catalyst- and reagent-controlled site-divergent intermolecular functionalization of C(sp 3)–H bonds, the factors responsible for modulating the site selectivity of these reactions, and will identify potential areas worthy of future research in this field.

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C(sp3)-H键的催化剂和试剂控制的位点发散分子间官能化的进展

摘要 分子间 C(sp 3)-H 键官能化反应有望通过在以前的惰性位点引入官能团来彻底改变我们合成有机分子的方式。然而，该研究领域的最大挑战之一是位点选择性，其中所选的 C(sp 3)-H 键必须被选择性功能化，并且其他具有类似立体电子特性的 C(sp 3)-H 键必须保持完整。为了解决这个问题，化学家开发了一些方法，这些方法依赖于针对天生更具反应性的 C(sp 3)–H 键或使用预先安装的官能团将催化剂或试剂导向特定的 C(sp 3)–H 键。然而，这些方法的适用性总是有限的，因为只有少数固有的反应性 C(sp 3)-H 键或那些靠近某些官能团的键可以以良好的位点选择性进行功能化。为了克服这些限制，化学家还开发了控制 C(sp 3)–H 键官能化位点的催化剂和试剂，并开始释放这些反应的潜力，以实现 C(sp 3)– 的位点发散功能化。 H 键，其中通过调节催化剂或试剂的立体电子特性来改变官能化位点。这篇简短的评论将总结催化剂和试剂控制的 C(sp 3)-H 键的位点发散分子间官能化的选定例子，这些因素负责调节这些反应的位点选择性，