Three different aminonaphthoquinones of great interest in medicinal chemistry due to their diverse biological activities were more efficiently synthesized and characterized starting from naphthoquinones with hydrazoic acid in the presence of ceric ammonium nitrate (CAN). We have previously reported a highly time demand synthesis of 2-amino-1,4-naphthoquinone and 2-amino-3-methyl-1,4-naphthoquinone in the absence of the CAN catalyst. In the current study, we have also obtained 3-amino-5-hydroxy-1,4-naphthoquinone and reduced all reaction times in the presence of CAN as a catalyst. Reaction rates have been increased to circa three times their original times. All aminonaphthoquinones have been characterized by NMR, vibrational, and chromatographic techniques. Additionally, we have proposed a reaction mechanism for the amination of naphthoquinone derivatives in an acid medium, based on in-depth DFT calculations.