Abstract A novel methodology for the efficient and selective synthesis of isomers A and B of N-substituted dihydrodipyridopyrazines was developed. The key step is the intermolecular coupling of aminopyridines and halonitropyridines/dihalopyridines in the presence of a catalyst system composed of Pd (OAc) 2/Xantphos. This system displays good functional group compatibility and the desired C–N bond-forming process proceeds in good yields. ...