36 cis-デカリン系セスキテルペン類の合成

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概要

• 論文の詳細を見る

• cis-Decaline-type sesquiterpines, 4α-hydroxyisochamaecynone and (-)occidentalol, were synthesized in the following manner. 1) 4α-Hydroxyisochamaecynone (Ib) and its 4-epi-isomer (VII) were synthesized from the acetylenic ketone (II) which was prepared from 1-santonin through nine step reactions. Enolacetylation of II, followed by epoxidation gave an epoxide (IV), hydrolysis of which gave a hydroxyketone (V). Bromination of V and successive dehydro-bromination afforded 4β-hydroxychamaecynone (VII). Thermal rearrangement of the epoxide (IV), followed by hydrolysis gave a hydroxyketone (IX); the C_4-epimer of V. Bromination of IX and successive dehydro bromination gave 4α-hydroxyisochamaecynone (Ib) which is identical with naturally occurring "hydroxyisochamaecynone". 2) (-)Occidentalol (XVc) and its 7-epi-isomer (XVa) were synthesized from the ketone (XVI) which was derived from 1-santonin. Oxidation of XVI with OsO_4-NaIO_4, followed by oxidation with Ag_2O and then methylation gave an ester (XIX). Bromination of XIX, followed by dehydrobromination gave a mixture of unsaturated ketones (XXII and XXIII), reduction of which with NaBH_4 and succesive dehydration with Al_2O_3-Py afforded a diene (XXV). Treatment of XXV with CH_3MgI afforded an alcohol (XVa), which is not identical with occidentalol. Epimerization of XXV with t-BuOK, followed by hydrolysis and methylation gave a diene(XXVII); the C_7-epimer of the diene (XXV). Treatment of XXVII with CH_3MgI afforded (-)occidentalol (XVc), which is an antipide of naturally occurring (+)occidentalol.

• 天然有機化合物討論会の論文
• 1969-09-01

著者

• 安東 政義

  東北大理

• 高瀬 嘉平

  Department of Chemistry, Faculty of Science, Tohoku University

• 高瀬 嘉平

  東北大理

• 七海 憲

  東北大理

• 中川 透

  東北大理

• 浅尾 豊信

  東北大理

• 高瀬 嘉平

  Department Of Chemistry Faculty Of Science Tohoku University

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