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DOI: 10.1055/s-0043-1773090
Total Synthesis of (–)-Magellanine
First Total Synthesis of Lycopodium Alkaloids of the Magellanane Group. Enantioselective Total Syntheses of (–)-Magellanine and (+)-Magellaninone.
J. Am. Chem. Soc. 1993;
115: 2992-2993
DOI: 10.1021/ja00060a064
Key words
(–)-magellanine - Lycopodium alkaloids - Cohen ring expansion - Birch reduction - Prins-pinacol rearrangement - Lemieux–Johnson reaction - Saegusa–Ito oxidation
Significance
In 1993, Overman and co-workers present the enantioselective total synthesis of (–)-magellanine, isolated from Lycopodium magellanicum. Salient features of the natural product include a congested 6-5-5 ring-fused system, as well as a piperidine ring. Biosynthetically related to the fawcettimines, (–)-magellanine is thought to be derived from the amino acid lysine.
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Comment
The synthesis hinges on and showcases a Prins-pinacol rearrangement to access tetracycle F, setting the central quaternary carbon center, as well as forging the carbocyclic core. Subsequent Johnson–Lemieux reaction and reductive amination grant access to the piperidine ring present in the natural product. Finally, methyl 1,4-addition, desaturation, Boc deprotection, and amine methylation, followed by silyl deprotection, afford (–)-magellanine.
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Publikationsverlauf
Artikel online veröffentlicht:
14. Februar 2024
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