Trifluoromethanesulfonyl‐Based Reagents: Novel Synthetic Strategies and Mechanistic Insights for Trifluoromethylation Transformations

Trifluoromethylated compounds act as indispensable synthetic building blocks in the fields of agrochemicals, pharmaceuticals, and functional materials, by virtue of their tunable lipophilicity, enhanced cell membrane permeability and superior metabolic stability. The distinctive physicochemical characteristics of the trifluoromethyl group have stimulated tremendous research interest in developing efficient, site‐selective, and scalable synthetic methodologies for the trifluoromethylation of diverse organic molecular skeletons. Over recent years, trifluoromethanesulfonyl‐derived trifluoromethylating reagents have arisen as versatile, bench‐stable, and easily accessible CF 3 sources, facilitating the development of numerous green, atom‐economic, and mild synthetic strategies to access structurally varied trifluoromethylated compounds and functional molecular scaffolds. This review systematically summarizes the advances in catalytic trifluoromethylation reactions enabled by trifluoromethanesulfonyl derivatives, which are categorized into four main types: photoredox catalysis, electrochemical catalysis, metal‐free catalysis, and transition‐metal catalysis for trifluoromethylation transformations.