Enabling Site-Selective C–H Functionalization of Aliphatic Alcohols and Amines with exo-Directing Groups by Tether-Tunable Design of Pd^II/Pd^IV Catalysis

We report herein a general platform for palladium catalysis using a library of cyclic diacyl peroxides, achieving site-selective C–H functionalization of aliphatic alcohols and amines. Experimental studies and theoretical calculations indicate that bystanding cyclic diacyl peroxides minimize unwanted reductive elimination events and enable controlled C–H cleavage. The protocol is simple and scalable and offers high selectivity and a broad range of substrates and nucleophiles, including complex molecules. The findings advance understanding of high-valent palladium chemistry, providing a tool for creating chemically diverse vicinal diols and amino alcohols and opening new possibilities in C–H functionalization.