Benzannulation of phthalic anhydrides with alkynes to polyfunctionalized naphthalenes and phenanthrenes was confirmed to be straightforward using a palladium catalytic system. Sequential liberation of CO2 and CO occurred via oxidative decomposition of anhydride. In the case of 1,8-naphthalenedicarboxylic anhydrides, both aryls were encompassed in the annulation reaction to afford acenaphthylenes.

A novel method for the decarboxylative and decarbonylative addition of cyclic anhydrides to alkynes is developed.