Control of site selectivity is an exciting direction for synthetic organic chemistry owing to the possibility of selective modification of multifunctionalized molecules, ultimately including biomacromolecules. In this review, our recent research related to site selectivity in two types of transformation, namely, the acylation of hydroxy groups and C–H amination, is summarized. Regarding the acylation of hydroxy groups, catalyst-controlled site selectivity enables unconventional retrosynthetic analysis, leading to efficient syntheses of sugar-related natural and unnatural products. Regarding C–H amination, the discovery of unprecedented reaction sites in intermolecular amination mediated by dirhodium nitrenes is described. The findings of this research demonstrate the power of site-selective transformation in the synthesis of a particular class of compounds.

由于多功能分子（最终包括生物大分子）的选择性修饰的可能性，位点选择性的控制是合成有机化学的一个令人兴奋的方向。在这篇综述中，我们总结了我们最近关于两种类型转化中位点选择性的研究，即羟基的酰化和 C-H 胺化。关于羟基的酰化，催化剂控制的位点选择性使非常规逆合成分析成为可能，从而实现与糖相关的天然和非天然产物的有效合成。关于 C-H 胺化，描述了在氮烯二铑介导的分子间胺化中发现了前所未有的反应位点。