Substitution-with-Allylic-Rearrangement Reactions of Glycal Derivatives

Abstract

A review with 106 refs. Glycals (or usually their O-substituted derivs.) are readily converted into 2,3-unsatd. glycosyl compds. with O-, C-, N-, S- or otherwise linked substituents at the anomeric position. These products have been found to be useful for a range of synthetic purposes. In particular, the C-glycosidic compds. have served as readily available starting materials for the prepn. of useful non-carbohydrate compds. While these allylic rearrangement processes are usually conducted under the influence of Lewis acid catalysts, adaptations that involve activation of the allylic substituents of the starting glycals as leaving groups under neutral conditions have been developed. General features of the reactions are described as well as applications in synthesis and extensions of the basic processes. [on SciFinder(R)]