Chemo‐ and Regio‐selective Dual‐Functionalization of Arenes: Synthesis of Multi‐Functional Aromatics via Aromaticity Destruction‐Reconstruction Process

Abstract Dual functionalizations of arenes promise to remain a powerful and versatile strategy for the synthesis of complex molecules with diverse applications in various fields. Dearomatization‐Functionalization‐rearomatization strategy emerges as a versatile tool for chemo‐ and regioselective functionalization of arenes via 2,5‐cyclohexadienone/2,5‐cyclohexadienimines, which can be easily accessible from phenols or anilines. 2,5‐Cyclohexadienones serve as an “aromatic to be” synthon with multiple electrophilic centres, providing an opportunity towards their functionalization. While mono‐functionalization was widely explored and covered in literature, simultaneous dual functionalizations with two distinct coupling partners offer a powerful strategy for rapid molecular diversification around aromatic rings. Diverse functional groups/coupling partners have been introduced chemo‐ and regio‐selectively. The synthetic processes adopted are generally sustainable and free from transition metals and exotic conditions. This review showcased the advancement in developing dual functionalizations of phenols/anilines for the site‐selective synthesis of multi‐functional arenes through an aromaticity‐destruction‐functionalization‐construction strategy.