Aryl sulfonium salts have exhibited obvious advantages such as simple preparation, structural diversity, good site- selectivity, and rich reactivity, and have emerged as important intermediates for the precise functionalization of arenes. In recent years, aryl sulfonium salts have been widely utilized in fluorination and fluoroalkylation reactions, among which cyclic aryl sulfonium salts such as thianthrenium, phenoxathiinium, dibenzothiophenium, and phenothiazinium salts have attracted particular attention. This article comprehensively summarizes the progress in fluorination and fluoroalkylation reactions of aryl sulfonium salts, which are mainly categorized into three types: (1) Construction of Ar—F and Ar—[¹⁸F] bonds via transition-metal- and visible-light-catalyzed fluorination and aromatic nucleophilic substitution with radioactive [¹⁸F] salts; (2) Formation of Ar—CF₂H, Ar—CF₂COR, Ar—CF₃, and Ar—CF(CF₃)₂ bonds through transition-metal-catalyzed couplings, catalyst-free couplings, and photoinduced radical couplings; (3) Construction of Ar—OCF₃, Ar—SCF₃, Ar—SeCF₃, and Ar—TeCF₃ bonds, involving reaction mechanisms such as transition-metal catalysis, mechanochemical transformations, and photocatalytic activation of electron donor-acceptor (EDA) complexes. These reactions provide important references for the further applications of aryl sulfonium salts in fluorine chemistry.

Key words: aryl sulfonium salts, fluorination, [¹⁸F]-labeling, fluoroalkylation