ABSTRACT
This chapter covers the formation of epoxides from allyl alcohols and derivatives. It discusses the reactions of 2,3-epoxy alcohols, omitting the methodology used to prepare the epoxide. The chapter also covers epoxidation reactions of other functionalized alkenes and the reactions of the resultant epoxides. It deals with oxidation reactions that provide diols from alkenes. The epoxidation of allyl alcohols catalyzed by tungsten proceeds with retention of configuration at the reaction centers. Reactivity towards the reagent is directly related to the nucleo-philicity of the alkene; allyl alcohols are more reactive than homoallyl alcohols. The ability of the Sharpless epoxidation catalyst to differentiate between the two enantiomers of an asymmetric allyl alcohol affords a powerful synthetic tool to obtain optically pure materials through kinetic resolution. The heavy dependence of the resultant stereochemistry upon the substituents of an allyl alcohol has made metal mediated oxidations preferable to the use of peroxy acids.
