Collective Total Synthesis of Tetracyclic Diquinane Lycopodium Alkaloids (+)-Paniculatine, (−)-Magellanine, (+)-Magellaninone and Analogues Thereof

The collective total synthesis of tetracyclic diquinane Lycopodium alkaloids, (+)-paniculatine, (−)-magellanine, (+)-magellaninone, and two analogues (−)-13-epi-paniculatine and (+)-3-hydroxyl-13-dehydro-paniculatine, has been accomplished. By logic-guided addition of a strategically useful hydroxyl group at C-3 of paniculatine, the formidable tetracyclic core was rapidly synthesized utilizing a site-specific and stereoselective aldol cyclization, thus making the ABD → ABCD tetracyclic approach to diquinane Lycopodium alkaloids attainable for the first time.