Total Syntheses of Bisdehydroneostemoninine and Bisdehydrostemoninine by Catalytic Carbonylative Spirolactonization

The first total syntheses of the stemona alkaloids bisdehydroneostemoninine and bisdehydrostemoninine in racemic forms have been achieved. The synthetic strategy features a novel palladium‐catalyzed carbonylative spirolactonization of a hydroxycyclopropanol to rapidly construct the oxaspirolactone moiety. It also features a Lewis acid promoted tandem Friedel–Crafts cyclization and lactonization to form the 5‐7‐5 tricyclic core of the target stemona alkaloids. Core strength: The first total syntheses of the stemona alkaloids bisdehydroneostemoninine and bisdehydrostemoninine are reported. The synthesis features a novel palladium‐catalyzed carbonylative spirolactonization to rapidly construct the oxaspirolactone moiety and a Lewis acid promoted tandem Friedel–Crafts cyclization and lactonization to form the 5‐7‐5 tricyclic core of the target alkaloids.