The synthesis of a series of novel indazole-5,6-diamine derivatives is described. This indazole ring system was incorporated in an octahydropyrrolo[3,4-b]phenazine scaffold and was diversely and regioselectively substituted on the nitrogen atoms at the 5- and 10-positions. Thus, the nitrogen atom at the 5-position was found to be more reactive toward electrophiles than the one at the 10-position. This difference of reactivity could be attributed to the electronic effect of the pyrazole moiety. Moreover, an unexpected tetrahydropyran protecting group migration was observed from the N-1 atom to the C-11 position of the octahydropyrrolo[3,4-b]phenazine scaffold.