10 リコポジウムアルカロイドの合成研究 : (±)-Anhydrolycodoline及び(±)-Lycopodineの全合成

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概要

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• The total synthesis of (±)-anhydrolycodoline has been reported. The Michael reaction of the keto-ester(5) with acrolein proceeded stereospecifically to give the aldehyde(6) that was cyclized to afford the keto-ols(7), in which the methyl group has the same configuration with that of the natural base. Introduction of the nitrogen function to the bridge-head of the keto-acid(17) was achieved by the modified Curtius reaction to give the urethane(18b), which was converted to the tricyclic amino-ketone(25) in 6 steps. On the other hand, treatment of 18b with dimethylsulfonium methylide afforded stereoselectively the oxirane(28) followed by reaction with malonic ester to give the lactone(29b). The amino-lactone(30) was treated with Triton B in boiling ethanol to afford the tricyclic lactam(31). Hydroboration of the urethane(33b), prepared from 31, afforded the diol(34b) regio- and stereoselectively, which was transformed to the acrylyl amide(41) in 3 steps. Unfortunately, the intramolecular Michael-type cyclization of 41 to the lactam(42) for lycodoline did not take place for a stereoelectronic reason. Dehydration of 41 with conc. sulfuric acid afforded the anhydro-amide(45), which was cyclized smoothly in the presence of sodium ethoxide and 18-crown-6 to give the tetracyclic lactam(46). Reduction of 46 with lithium aluminum hydride followed by oxidation with Jones reagent yielded (±)-anhydrolycodoline. This work also amounts to a formal total synthesis of (±)-lycopodine.

• 天然有機化合物討論会の論文
• 1978-08-22

著者

• 今西 武

  Faculty Of Pharmaceutical Sciences Osaka University

• 今西 武

  阪大薬

• 金 相元

  Faculty Of Pharmaceutical Sciences Josai University

• 堀井 善一

  Faculty Of Pharmaceutical Sciences Josai University

• Kim S‐w

  Faculty Of Pharmaceutical Sciences Josai University

• 百瀬 雄章

  (present Address)faculty Of Pharmaceutical Sciences Toyama Medical And Pharmaceutical University

• 金 相元

  城西大薬

• 坂東 幸英

  城西大薬

• 高橋 延子

  城西大薬

• 堀井 善一

  城西大薬

• 二宮 一弥

  阪大薬

• 百瀬 雄章

  阪大薬

• 坂東 幸英

  Faculty Of Pharmaceutical Sciences Josai University

• 二宮 一弥

  阪大薬:(現)神戸女子薬科大学

• 高橋 延子

  Faculty Of Pharmaceutical Sciences Josai University

• 百瀬 雄章

  Faculty Of Pharmaceutical Sciences Kanazawa University

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