Asymmetric Epoxidation of Allylic Alcohols: The Katsuki-Sharpless Epoxidation Reaction

Katsuki, Tsutomu; Martin, Victor S.


In 1980, Sharpless and Katsuki discovered a system for the asymmetric epoxidation of primary allylic alcohols that utilizes Ti(OPr-i)4, a dialkyl tartrate as a chiral ligand, and tert-butyl hydroperoxide as the oxidant. Notably, this reaction exhibits high levels of enantioselectivity (usually > 90% ee). Like other metal-catalyzed epoxidations, this reaction also proceeds under mild conditions with good chemical yield and with high regio- and chemoselectivity. Various aspects of this reaction, including its mechanism, early synthetic applications, and further transformations of the epoxy alcohol product, have been reviewed. In this chapter, the full scope and limitations of this reaction, its synthetic applications, and typical experimental conditions are described.