Polyfunctional tetrahydropyrido [2, 3-b] pyrazine scaffolds can be synthesized by sequential reaction of pentafluoropyridine with sodium phenylsulfinate and an appropriate diamine. The polyfunctionality possessed by the difluorinated tetrahydropyrido [2, 3-b] pyrazine scaffolds was demonstrated in selected model reactions with nucleophiles to give access to various polysubstituted [6, 6]-ring fused systems.