An efficient palladium-catalyzed route for the synthesis of benzimidazole-fused phenanthridines from o-dibromoarenes and 2-arylbenzimidazoles is described. The sequentially accomplished reaction comprises intermolecular C-H arylation of 2-arylbenzimidazoles followed by an intramolecular N-arylation reaction promoted by the same Pd catalyst. This Pd-catalyzed double arylation provides a useful tool for the discovery of fluorescent materials.

An efficient "one-pot" route for the synthesis of benzo[4,5]imidazo[2,1-a] isoquinolines has been developed via nucleophilic addition of 2-aryl benzimidazoles to alkynyl bromides and subsequent palladium-catalyzed intramolecular C-H vinylation.

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