Asymmetric Total Synthesis of (+)‐Mannolide C

Abstract (+)‐Mannolide C is a complex hexacyclic C 20 cephalotane‐type diterpenoid featuring a highly strained 7/6/6/5 tetracyclic core containing eight consecutive stereocenters and two bridging lactones. The first asymmetric total synthesis of (+)‐mannolide C has been accomplished by lipase‐mediated resolution, Ru‐complex‐catalyzed double ring‐closing metathesis (RCM) reactions, Ni II ‐catalyzed diastereoselective Michael addition, and Mn III ‐catalyzed allylic oxidation as the key transformations.