Diastereoselective Total Synthesis of (±)‐Toxicodenane A

Abstract

The first total synthesis of tricyclic sesquiterpene (±)‐toxicodenane A has been accomplished. This synthetic work was completed in 12 steps from dimedone through diastereoselective reductive desymmetrization of 2,2‐disubstituted 5,5‐dimethylcyclohexane‐1,3‐dione, stereocontrolled allylation, ring‐closing metathesis of a diene compound to yield bicyclic compounds that bear a seven‐membered ring, and construction of the oxygen‐bridged moiety through neighboring group assisted ring‐opening reaction of an epoxide as key steps.