Abstract

Abstract Cycloaddition reactions involving arynes provide privileged strategies for the convergent synthesis of polycyclic compounds containing aromatic rings. This review focuses on the application of aryne chemistry, in particular [4+2] and palladium‐catalysed [2+2+2] cycloaddition reactions, in the synthesis of large polycyclic aromatic hydrocarbons (PAHs) containing five or more fused benzene rings. Many of the polycyclic compounds included in this report display properties of interest in the field of materials science and some can be considered as nano‐sized graphene substructures or nanographenes.