The enantioselective synthesis of cytostatic and antibiotic xanthatin (1 a) is reported. As a key intermediate, a bicyclic compound 2 was identified, which can be readily synthesized from methyl‐2‐furoic acid in diastereo‐ and enantiomerically pure form. Compound 2 can be functionalized regio‐ and stereoselectively at C‐6 and C‐7, allowing the facile introduction of the functionalities found in xanthatin, as well as the synthesis of derivatives thereof. Moreover, a robust strategy for the introduction of the exo‐methylene group at C‐3, commonly found in many sesquiterpenes, was developed that makes use of masking the alkene in the α,β‐unsaturated carbonyl system by O‐pivaoyl, which is stable under acidic and mild basic conditions but eliminated upon treatment with strong bases.