An efficient method was developed for the synthesis of tetra(spirocycloalkane)-substituted α,ω-di(1,2,4,5,7,8-hexaoxa-10-azacycloundecan-10-yl)alkanes by a ring transformation reaction of 3,6-di(spirocycloalkane)-substituted 1,2,4,5,7,8,10-heptaoxacycloundecanes with α,ω-alkanediamines (1,4-butane-, 1,5-pentane-, 1,7-heptane-, 1,8-octane- and 1,10-decanediamines) catalyzed by Sm(NO3)3/γ-Al2O3. Using flow cytometry, it was shown for the first time that synthesized dimeric azatriperoxides are efficient apoptosis inducers with Jurkat, K562, U937, and Hek296.