Abstract A novel synthesis of highly fused perimidine derivatives was achieved in two steps from 2-alkynylbenzaldehydes. Copper-catalyzed annulation of 2-[(2-bromophenyl) ethynyl] benzaldehydes with 1, 8-diaminonaphthalene produced dihydroisoquinolino [2, 1-a] perimidines bearing a 2-bromophenyl group. Subsequent palladium-catalyzed C–H arylation provided dibenzo [1, 2: 7, 8] quinolizino [3, 4, 5, 6-kla] perimidine derivatives in ...