Total Synthesis of (±)-Jujuyane.

The first total synthesis of (±)-jujuyane, a cyclooctanoid natural product, was accomplished from a (5 + 3) dimerization product of oxidopyrylium ylide that forms the cyclooctanoid core structure along with inherited stereochemical bias. Selective functional group modifications of the highly oxygenated dimeric structure, followed by the tactical functional group manipulation around the eight-membered carbocyclic core, enabled the total synthesis of (±)-jujuyane, which will serve a guide for future applications of oxidopyrylium dimers to the natural product total synthesis.