From Common Carbohydrates to Enantiopure Cyclooctane Polyols and Glycomimetics via Deoxygenative Zirconocene Ring Contraction

d-Arabinose and d-glucose are transformed into the identical vinyl furanoside, whose role is to serve as the precursor to enantiopure cyclooctadienone 6. The key steps of this relay involve a zirconocene-promoted ring contraction and [3,3] sigmatropic rearrangement of an enynol. Subsequently defined are convenient synthetic routes to several cyclooctane-1,2,3-triols, 1,2,3,4,5-pentaols, and structurally related glycomimetics.