Details

Autor(en) / Beteiligte

• Itoh, Naoya
• Iwata, Takashi
• Sugihara, Hiromi
• Inagaki, Fuyuhiko
• Mukai, Chisato

Titel

Total Syntheses of (±)-Fawcettimine, (±)-Fawcettidine, (±)-Lycoflexine, and (±)-Lycoposerramine-Q

Ist Teil von

• Chemistry : a European journal, 2013-06, Vol.19 (26), p.8665-8672

Ort / Verlag

Weinheim: WILEY-VCH Verlag

Erscheinungsjahr

2013

Quelle

Wiley-Blackwell Journals

Beschreibungen/Notizen

• The total syntheses of four fawcettimine‐related Lycopodium alkaloids, (±)‐fawcettimine, (±)‐fawcettidine, (±)‐lycoposerramine‐Q, and (±)‐lycoflexine, were completed in a highly stereoselective manner. The Pauson–Khand reaction of 4‐methylidene‐6‐siloxyoct‐1‐en‐7‐yne followed by regio‐ and stereoselective hydrogenation led to the short‐step preparation of the bicyclo[4.3.0]nonenone intermediate bearing a methyl group with the required stereochemistry. The subsequent chemical manipulation of the bicyclic compound afforded the 6‐5‐9‐membered tricyclic dioxo compound, which was then transformed into the four targeted alkaloids in an alternative and more efficient fashion. Fawcettimine alkaloids: The total syntheses of four fawcettimine‐related Lycopodium alkaloids, (±)‐fawcettimine, (±)‐fawcettidine, (±)‐lycoposerramine‐Q, and (±)‐lycoflexine, are described. The key steps in these syntheses are the Pauson–Khand reaction of 4‐methylidene‐6‐siloxyoct‐1‐en‐7‐yne followed by regio‐ and stereoselective hydrogenation to provide the bicyclo[4.3.0]nonenone intermediate bearing a methyl group with the required stereochemistry (see scheme).