An original strategy toward bridged tetraoxazaspirobicycloalkanes was developed. The synthesis is based on a three-component condensation-cyclization reaction of primary arylamines with 1,1'-peroxybis (1-hydroperoxycycloalkanes) and pentane-1,5-dial catalyzed by Sm(NO3)3·6H2O. The structures and conformations of the products were determined by X-ray diffraction analysis and 1H and 13C NMR spectroscopy. High cytotoxic activity and biological potential toward ferroptosis induction were found for the synthesized bicyclic aza-peroxides.