Alternatively, radical-based intermolecular three-component approaches have emerged as a promising strategy for achieving alkene 1,2-aryl heteroatom functionalization (Figure 1A, ii). One of the classical methods is the Meerwein arylation that involves a reductive generation of aryl radicals from highly reactive precursors (aryldiazonium or diaryliodonium salts), followed by radical-polar crossover and trapping of the resulting carbocation with excess nucleophiles. In 2021, the Gaunt group reported an excellent study on the vicinal azidoarylation of alkenes using diaryliodonium salts as aryl radical sources and NaN3 as the heteroatom source, via a visible-light-mediated dual copper catalysis, to access -aryl azidoalkanes. However, the use of these reactive radical precursors presents challenges for the late-stage modification of complex bioactive molecules due to difficulties in accessing them. Conversely, readily available (hetero)arenes, which are prevalent in pharmaceutically relevant molecules, represent ideal aryl radical precursors (Figure ). However, generating aryl radicals through direct hydrogen atom abstraction of arenes is extremely challenging due to their high bond dissociation energy and site selectivity issues. To overcome this challenge, an elegant indirect approach using arylthianthrenium salts as aryl radical precursors was introduced by Ritter and co-workers in 2019, and it has since been widely employed in two-component reactions. The air and bench-stable arylthianthrenium salts can be derived from (hetero)arenes with excellent yield and site selectivity through electrophilic thianthrenation or a complementary Ir-catalyzed regioselective borylation followed by Cu-mediated thianthrenation for late-stage functionalization of complex bioactive molecules. More recently, Ritter and coworkers extended the application of this strategy to three-component reactions, enabling bromoarylation and aminoarylation of alkenes through photoredox and copper dual catalysis. Despite these recent advances, the development of a unified synthetic platform capable of rapidly assembling diverse 1,2-aryl heteroatomic compounds from inexpensive and readily available aromatics as well as olefins remains an unmet challenge.