Total synthesis of salvinorin A (1), a densely functionalized neoclerodane diterpenoid, having the most potent hallucinogenic activity and a selective κ–opioid agonist, has been completed in 20 steps starting from enantiomerically–pure Wieland–Miescher ketone derivative 23. Subsequently, alternative total synthesis of salvinorin A (1) has been developed via palladium–catalyzed double...