Synthesis of Polybenzoacenes: Annulative Dimerization of Phenylene Triflate by Twofold C-H Activation

Polycyclic aromatic hydrocarbons (PAHs) represent an emerging class of pi-conjugated molecules in the area of optoelectronic devices and materials. Unprecedented synthetic routes to various PAHs from simple phenol derivatives by a palladium-catalyzed annulative dimerization of phenylene triflate through twofold inter- and intramolecular C-H activation have been established. The initially formed partially fused PAHs can be smoothly transformed into a variety of fully fused PAHs by the Scholl reaction. Furthermore, the reactions of phenanthrene-substituted aryl triflates proceeded regioselectively. The findings inspired the development of a rapid and efficient synthesis of polybenzoacene derivatives. This study not only allows transformation of phenyl triflates, but also discloses a new retrosynthetic strategy towards PAHs, especially polybenzoacenes.