Stereoselective synthesis of protected l- and d-dideoxysugars and analogues via Prins cyclisations.

A de novo approach for the rapid construction of orthogonally protected l- and d-deoxysugars and analogues is described. A novel and robust silicon-acetal undergoes Prins cyclisations with a series of homoallylic alcohols in high yield and excellent stereocontrol. Modified Tamao-Fleming oxidation of the resulting silyltetrahydropyrans gives direct access to deoxyglycoside analogues and the approach was showcased in the synthesis of protected l-oliose, a component of the anticancer agent aclacinomycin A.