Rapid Access to Nanographenes and Fused Heteroaromatics by Palladium‐Catalyzed Annulative π‐Extension Reaction of Unfunctionalized Aromatics with Diiodobiaryls

Efficient and rapid access to nanographenes and π-extended fused heteroaromatics is important in materials science. Herein, we report a palladium-catalyzed efficient one-step annulative π-extension (APEX) reaction of polycyclic aromatic hydrocarbons (PAHs) and heteroaromatics, producing various π-extended aromatics. In the presence of a cationic Pd complex, triflic acid, silver pivalate, and diiodobiaryls, diverse unfunctionalized PAHs and heteroaromatics were directly transformed into larger PAHs, nanographenes, and π-extended fused heteroaromatics in a single step. In the reactions that afford [5]helicene substructures, simultaneous dehydrogenative ring closures occur at the fjord regions to form unprecedented larger nanographenes. This successive APEX reaction is notable as it stiches five aryl–aryl bonds by C−H functionalization in a single operation. Moreover, the unique molecular structures, crystal-packing structures, photophysical properties, and frontier molecular orbitals of the thus-formed nanographenes were elucidated.