Annulation reactions of electrophilic benzannulated heterocycles towards heteroacenes

The current review describes different annulation strategies reported with electrophilic benzannulated heterocycles for accessing heteroacenes. For the past two decades, the chemistry of electrophilic benzannulated heterocycles was extensively investigated, and several dipolar cycloadditions, metal and organo-catalyzed transformations were introduced for the generation of fused heterocycles. In this review, we have collected all the reports where the annulation of electrophilic benzannulated heterocycles results in a fully aromatic system, viz. heteroacenes with tri-, tetra-, and pentacyclic rings. We reviewed every paper on the synthesis of fused heterocycles that was accessible and categorized the review into several parts based on the electrophilic benzannulated heterocycle used in the heteroacene synthesis such as electrophilic indole, electrophilic benzothiophene, and so forth. The generality and mechanistic postulates of each methodology are highlighted. In addition, we have also tried to feature the advantages or shortcomings of each method and have mentioned the possible applications of these methodologies for accessing heteroacenes for material applications. This feature article describes the different annulation strategies with electrophilic benzannulated heterocycles for accessing heteroacenes (polyring fused heterocycles) reported from 1996 to date.