Solanum‐Alkaloide, XXIII1). Synthese von Solanum‐Alkaloiden aus 16β‐Hydroxy‐pregnan‐derivaten
- 29 August 1963
- journal article
- research article
- Published by Wiley in European Journal of Organic Chemistry
- Vol. 666 (1) , 155-176
- https://doi.org/10.1002/jlac.19636660120
Abstract
Die Umsetzung von 3β.16β‐Diacetoxy‐5α‐pregnan‐20‐on (IV) mit 2‐Lithium‐5‐methyl‐pyridin und anschließende Acetylierung führten zu (20R)‐3β.16β‐Diacetoxy‐20‐[5‐methyl‐pyridyl‐(2)]‐5α‐pregnan‐20‐ol (VIb), das nach Dehydratisierung Δ20‐3β.16β‐Diacetoxy‐20‐[5‐methyl‐pyridyl‐(2)]‐5α‐pregnen (VIIa) ergibt. Dessen katalytische Hydrierung vor oder nach alkalischer Hydrolyse liefert hauptsächlich (22s.25R)‐22.26‐Imino‐5α‐cholestan‐3β.16β‐diol (Tetrahydro‐solasodin A, XII) bzw. das (25s)‐Stereoisomere XIII (Dihydro‐tomatidin A). Behandlung der entsprechenden N‐Chlor‐Derivate mit Natriummethylat führt zu den Spiro‐aminoketal‐Alkaloiden Soladulcidin (XVIII) bzw. Tomatidin (XXI). Damit sind die genannten und weitere Solanum‐Steroidalkaloide über Pregnan‐Derivate formal totalsynthetisch zugänglich.Keywords
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