The study discloses that the redox activity of N-(1,4-naphthoquinone)-o-aminophenol derivatives ((LH2)-H-R) containing a (phenol)-NH-(1,4-naphthoquinone) fragment is notably different from that of a (phenol)-NH-(phenol) precursor. The former is a platform for a redox cascade. (LH2)-H-R is redox noninnocent and exists in Cat-N-(1,4-naphthoquinone)(2-) (LR2-) and SQ-N-(1,4-naphthoquinone) (L-R) states in the complexes. Reactions of (LH2)-H-R with cobalt(II) salts in MeOH in air promote a cascade affording spiro oxazine-oxazepine derivatives (L-OX(R)) in good yields, when R = H, Me, Bu-t. Spiro oxazine-oxazepine derivatives are bioactive, and such a molecule has so far not been isolated by a schematic route. In this context this cascade is significant. Dimerization of (LH2)-H-R -> L-OX(R) in MeOH is a (6H(+) + 6e) oxidation reaction and is composed of formations of four covalent bonds and 6-exo-trig and 7-endo-trig cyclization based on CO coupling reactions, where MeOH is the source of a proton and the ester function. It was established that the active cascade precursor is [(L-Me)(CoCl2)-Cl-III] (A). Notably, formation of a spiro derivative was not detected in CH3CN and the reaction ends up furnishing A. The route of the reaction is tunable by R, when R = NO2, it is a (2e + 4H(+)) oxidation reaction affording a dinuclear L-R2 complex of cobalt(III) of the type [(L-NO22)(2)Co-2(III)(OMe)(2)(H2O)(2)] (1) in good yields. No cascade occurs with zinc(II) ion even in MeOH and produces a L-Me complex of type [(L-Me)(ZnCl2)-Cl-II] (2). The intermediate A and 2 exhibit strong EPR signals at g = 2.008 and 1.999, confrming the existence of L-Me coordinated to low-spin cobalt(III) and zinc(II) ions. The intermediates of (LH2)-H-R -> L-OX(R) conversion were analyzed by ESI mass spectrometry. The molecular geometries of L-OX(R) and 1 were confirmed by X-ray crystallography, and the spectral features were elucidated by TD DFT calculations.