A highly selective method for the synthesis of N-allyl-tetraoxazocanes based on the Sm(III)-catalyzed recyclization of pentaoxaspiroalkanes with allylamine has been developed for the first time. A new reaction pathway for heptaoxadispiroalkanes has been established, which, under Sm(III) catalysis with allylamine, leads not to the expected recyclization but to selective cleavage with the formation of tetraoxazocanes and carbonyl compounds, expanding the understanding of the reactivity of polyperoxide systems. A method for the selective synthesis of previously inaccessible N-allyl-hexaoxazaspiroalkanes has been developed via the cycloaminomethylation of 1,1′-peroxybis(1-hydroperoxycycloalkanes) with 1,3,5-triallyl-1,3,5-triazinanone catalyzed by lanthanide complexes. A detailed comparative study of the conformational behavior of N-allyl derivatives has been conducted for the first time, showing a significant influence of the allyl substituent on the spatial organization and dynamics of the peroxide cycles, unlike their N-aryl analogs.
N. N. Makhmudiyarova (Thu,) studied this question.