Regioselective Hydroperoxylation of Aziridines and Epoxides Only with Aqueous Hydrogen Peroxide

A catalyst and organic solvent-free regioselective hydroperoxylation of aziridines and epoxides, including spiroaziridine- and spiroepoxy oxindoles have been explored with commercially available 50% aq. H2O2. This method provides an access to secondary benzylic beta-hydroperoxy amines and -alcohols and tertiary 3-hydroperoxy oxindoles. The protocol is also applicable to the less reactive alkyl aziridines. Furthermore, an acid-catalyzed Kornblum-DeLaMare type rearrangement of secondary benzylic hydroperoxide has also been revealed to afford amino- and hydroxyl ketones.

Automated summary

The catalyst and organic solvent-free regioselective hydroperoxylation method allows for the synthesis of secondary benzylic beta-hydroperoxy amines and alcohols, as well as tertiary 3-hydroperoxy oxindoles, and is also applicable to less reactive alkyl aziridines. Additionally, an acid-catalyzed Kornblum-DeLaMare type rearrangement of secondary benzylic hydroperoxide has been discovered to produce amino- and hydroxyl ketones.