Synthesis of Multiply Substituted Polycyclic Aromatic Hydrocarbons by Iridium‐Catalyzed Annulation of Ring‐Fused Benzocyclobutenol with Alkyne through C−C Bond Cleavage

The first iridium‐catalyzed intermolecular cyclization between alkynes and ring‐fused benzocyclobutenols (RBCB) through C−C bond cleavage is described. A variety of elusive polycyclic aromatic hydrocarbons (PAHs) with multiple substituents are obtained in good yields under mild conditions. This procedure provides a unique and expeditious tool for the synthesis of PAHs.