Olefin Epoxidation with α-Substituted Hydroperoxides

Article abstract of DOI:10.1021/ja00537a033

A number of α-substituted hydroperoxides were examined for their ability to epoxidize olefins in a stereospecific manner.Hydroperoxy ethers, amines, carbonyl compounds, and nitriles showed this capability.Intramolecular epoxidation was demonstrated in cases where ortho esters of some olefinic alcohols were treated with H2O2, and methyl orthooleate - H2O2 mixtures also epoxidized the internal olefin in an intramolecular reaction.Attempts to generate chiral hydroperoxides for asymmetric epoxidation are described and structural features required for epoxidation reagents are discussed.