A 10‐Year Journey Into Diverse Arylsulfonium Salts: Versatile Reagents for Organic Synthesis

As an important class of organosulfur reagents for many chemical transformations, arylsulfonium salts have featured obvious advantages such as good thermal stability, easy preparation, high structural diversity, and rich reactivity, showing the broader substrate scopes and better selectivity than other aryl pseudohalides. Over the past decade, our group has pioneered the arylsulfonium salt chemistry. Starting from Pd-catalyzed reactions with Yagupolskii-Umemoto reagents, we have established an array of arylation platforms with different types of arylsulfonium salts through transition-metal-mediated cross-couplings, catalyst-free reactions, and photoredox transformations. These reactions accommodate a wide range of carbon- and heteroatom-centered coupling partners, showing excellent functional group tolerance, and prove effective in the late-stage modification of structurally complex molecules. This account summarizes our efforts on the synthetic applications of arylsulfonium salts, demonstrating their great potential in modern organic synthesis.