Building blocks for syntheses of guaiane and secoguaiane sesquiterpenoids were prepared by the title reaction. 4-(3-Methylfuran-2-yl)butan-2-one (1) was obtained in five steps from methyl 3-methylfuran-2-carboxylate (4), and treatment of 1 with pentachloroacetone and sodium 2,2,3,3-tetrafluoropropoxide in 2,2,3,3-tetrafluoropropan-1-ol produced a [4 + 3] cycloadduct that was dechlorinated without prior isolation to give the oxabicyclic diketone 2 in a low yield. A better route to diketone 2 was via the oxabicycle 10b, prepared in a high yield from 2-(but-3-en-1-yl)-3-methylfuran (9) and pentachloroacetone, followed by dechlorination. Treatment of 2 with dilute methanolic potassium hydroxide resulted in the cleavage of the oxa bridge, with formation of 3,8-dimethylazulen-4-ol (11). Catalytic hydrogenation of 2 afforded the saturated oxabicyclic diketone 14, intramolecu-