Unlocking the Potential of Catalysts for Dearomatization of Heteroarenes

Abstract Catalytic dearomatization of aromatic heterocycles is a substantial tool for the synthesis of polycyclic molecules of high complexity by converting two‐dimensional, planar systems to three‐dimensional, highly functionalised molecules. However, this step is critical for the development of new heterocycles, which serve as key intermediates in the synthesis of agrochemicals, pharmaceuticals, and natural products. Nevertheless, catalytic dearomatization of heteroaromatic compounds is challenging owing to their intrinsic stability and low reactivity. Consequently, efficient catalytic systems, most commonly involving transition metals, nucleophilic additions, or photochemical methods are inevitable for this transformation. Despite the extensive literature on individual classes, a unified review encompassing the full range of “N”, “O”, and “S”‐based heterocycles remains unexplored. This review critically discussed the role of catalysts, and their mechanistic insights on dearomatization of heteroarenes over the period of last ten years. We have also addressed the major challenges related to overcoming catalyst selectivity, reaction optimization, and the incorporation of green chemistry principles, with a focus on the development of more efficient and sustainable catalytic processes.