Synthesis of new tetracyclic azaheteroaromatic cores via auto-tandem Pd-catalyzed and one-pot Pd- and Cu-catalyzed double C–N bond formation

Inter- and intramolecular transition metal-catalyzed amination of 2-chloro-3-iodopyridine and 2,3-dibromopyridine, respectively, with benzodiazinamines yielded six hitherto unknown tetracyclic azaheteroaromatic cores. C–N bond formation was achieved via auto-tandem (Pd-catalyst) as well as one-pot (sequential use of a Pd- and Cu-catalyst) catalysis.