4.1 Arenophile-Mediated Photochemical Dearomative Functionalization

Abstract Dearomatizations have long been recognized as an important class of reactions, with significant progress achieved; however, the utilization of simple and nonactivated arenes remains a challenging endeavor due to their inherent inertness and the difficulty of achieving selective transformations. This review highlights an emerging dearomatization approach that enables selective conversion of such arenes under mild conditions: arenophile-mediated photochemical dearomative functionalization. This methodology provides efficient access to alicyclic structures, offering both functional and stereochemical complexity, including C—C, C—B, C—N, C—O, and C—H bond formations. Applications in the synthesis of complex bioactive compounds are also presented to demonstrate the unique versatility of this strategy.