Total Synthesis of (±)-11-O-Debenzoyltashironin via Palladium-Catalyzed 5-endo Ene-yne Cyclization Enabled trans-5-6 Ring Fusion.

Illicium sesquiterpenes are a synthetically fascinating family of polycyclic natural products owing to their diversified pharmacological activities and structural complexity. Our cumulative efforts on developing a universal reductive coupling strategy toward stereoselective assembly of illicium sesquiterpenes recently resulted in a total synthesis of 11-O-debenzoyltashironin, a rare illicium sesquiterpene with a unique allo-cedrane carbon skeleton exhibiting prominent neurotropic activity, with complete stereochemical control. Our key tactics involved an unprecedented Pd(II)-catalyzed 5-endo ene-yne cyclization that directly allowed strained trans-5-6 ring fusion and a late-stage transannular McMurry coupling that furnished the compacted tetracyclic carbon skeleton rapidly.