First total synthesis of Lycopodium alkaloids of the magellanane group. Enantioselective total syntheses of (-)-magellanine and (+)-magellaninone

Molecular rearrangements in the construction of complex molecules

“…Graduate student Theodore Johnson, Jr., who succeeded Hirst on the project, successfully completed in late 1992 the inaugural total syntheses of (–)-magellanine ( 97 ) and the related ketone, (–)-magellaninone 114. Key stages of this synthesis are summarized in Scheme 20.…”

3.16 The Semipinacol Rearrangements

“…One typical example is the total syntheses of (-)-magellanine and (þ)-magellaninone achieved by Overman's group (Scheme 43). 52 The key carbotetracycle intermediate 82 was obtained through a Prins-pinacol rearrangement of compound 79. During this procedure, Prins cyclization of the oxocarbenium ion 80 from the less hindered convex face gave the b-siloxy carbenium ion 81, which underwent a semipinacol rearrangement to successfully install the crucial quaternary carbon stereocenter and construct the tetracyclic skeleton of the magellanane alkaloids.…”

Malycorins A-C, New Lycopodium Alkaloids from Lycopodium phlegmaria

“…These unique skeletons have also been challenging targets for total synthesis. [4][5][6][7][8] Among them, huperzine A is a highly specific and potent inhibitor of acetylcholinesterase (AChE).…”