Total Synthesis of (S)-(+)-Imperanene. Effective Use of Regio- andEnantioselective Intramolecular Carbon−Hydrogen InsertionReactions Catalyzed by Chiral Dirhodium(II) Carboxamidates
The total synthesis of (S)-(+)-imperanene, a natural product found in Chinese medicine, has beencompleted in 12 steps from a commercially available cinnamic acid. The key step is highlyenantioselective carbon−hydrogen insertion from a diazoacetate using a chiral dirhodium(II)carboxamidate catalyst. An elimination process essential to the construction has been optimizedto avoid intramolecular Friedel−Crafts alkylation.