We report the synthesis of chiral furanyl and pyranyl dienes 1 and 2 based on cycloalkenation ofchiral tungsten alkynol complexes. These two dienes bear a chiral 1,3-dioxolane group to controldiastereoselective Diels−Alder reactions with electron-deficient olefins. The chiral 1,3-dioxolanesubstituents of the cycloadducts were degraded into hydrogen atoms to make these molecules possesscommon furan and pyran rings. Dienes 1 and 2 are good building blocks for enantiopure forms oftricyclic oxygen compounds.