C-C Bond (Hetero)arylation of Ring-Fused Benzocyclobutenols and Application in the Assembly of Polycyclic Aromatic Hydrocarbons.

Herein, we disclose a new and efficient synthetic approach to triphenylene-based polycyclic aromatic hydrocarbons (PAHs) from ring-fused benzocyclobutenols (RBCBs) through the cleavage of the C-C σ-bond. Two key transformations are involved: (a) palladium-catalyzed C-C bond (hetero)arylation of RBCBs; and (b) Lewis acid-promoted intramolecular annulation leading to complex polycyclic compounds. A variety of multiply substituted triphenylenes and derivatives are obtained in synthetically useful yields.