Transition metal-catalyzed double ring closures of 1,1-diaryl-2,2-diethynylethylenes yield polycyclic aromatic hydrocarbons and heterocycles that contain a newly formed naphthalene ring system embedded in a larger polycyclic network. The diynes required for this procedure are readily synthesized from diaryl ketones by the Corey-Fuchs olefination and subsequent Sonogashira coupling with trimethylsilylacetylene followed by desilylation. This procedure provides easy access to new compounds such as 3,11-di-tert-butyl[4]helicene and 1,8,9-perinaphthothioxanthene. Double naphthoannulation of 9,10-anthraquinone by this procedure closes four new benzene rings in a single operation to give coronene, although the yield in this case is presently low.