An Approach to α‐ and β‐Amino Peroxides via Lewis Acid Catalyzed Ring Opening‐Peroxidation of Donor‐Acceptor Aziridines and N ‐Activated Aziridines

Site‐selective ring‐opening process of two different aziridine classes with hydroperoxide is described herein that provides access to various α‐ and β‐amino and α‐(imino)‐peroxy compounds. This strain‐release‐driven peroxide addition to aziridines represents an alternative approach for entries to biologically significant heteroatom substituted organic peroxides and complements existing methods in the field. The peroxide products obtained by this method displayed a different reactivity during peroxide‐specific rearrangement processes promoted by either acid or base. Mechanistic studies and useful synthetic elaboration of the products have also been presented.