Hypervalent aryliodoumiums are intensively investigated as arylating agents. They are excellent surrogates to aryl halides, and moreover they exhibit better reactivity, which allows the corresponding arylation reactions to be performed under mild conditions. In the past decades, acyclic aryliodoniums are widely explored as arylation agents. However, the unmet need for acyclic aryliodoniums is the improvement of their notoriously low reaction economy because the coproduced aryl iodides during the arylation are often wasted. Cyclic aryliodoniums have their intrinsic advantage in terms of reaction economy, and they have started to receive considerable attention due to their valuable synthetic applications to initiate cascade reactions, which can enable the construction of complex structures, including polycycles with potential pharmaceutical and functional properties. Here, we are summarizing the recent advances made in the research field of cyclic aryliodoniums, including the nascent design of aryliodonium species and their synthetic applications. First, the general preparation of typical diphenyl iodoniums is described, followed by the construction of heterocyclic iodoniums and monoaryl iodoniums. Then, the initiated arylations coupled with subsequent domino reactions are summarized to construct polycycles. Meanwhile, the advances in cyclic aryliodoniums for building biaryls including axial atropisomers are discussed in a systematic manner. Finally, a very recent advance of cyclic aryliodoniums employed as halogen-bonding organocatalysts is described.

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Atropisomeric biaryls are one of the important motifs which are highly essential in ligands, biologically active molecules, and natural products. For the synthesis of atropisomeric biaryl and vinylarene derivatives, the transition metal‐catalyzed CH functionalization has been documented as a promising strategy. This article is planned to summarize the research in the field of biaryl atropisomer synthesis within the scope of transition‐metal catalyzed CH bond functionalization. Research regarding atroposelectivity in CH activation procedures and the applications of these novel ideas for the improvement of new‐fashioned carbon–carbon and carbon–heteroatom bond‐featuring reactions are described. Throughout this article, a particular emphasis is placed on the development of CH functionalization strategies that are relevant in the reign of atroposelective synthesis of chiral biaryl and vinylarene analogs.