Asymmetric Total Synthesis of (+)-(3E)-Pinnatifidenyne via Abnormally Regioselective Pd(0)-Catalyzed Endocyclization.

摘要: The asymmetric total synthesis of the marine natural product (+)-(3E)-pinnatifidenyne was accomplished. key features involve construction an eight-membered cyclic ether by abnormally regioselective Pd(0)-catalyzed cyclization, installation a double bond in oxocene skeleton sequential situ deconjugative isomerization, and efficient introduction crucial chloride mediated substrate-controlled diastereoselective reduction.