56 dl-Pumiliotoxin Cの立体選択的合成

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概要

• 論文の詳細を見る

• Racemate of pumiliotoxin C (1) which is a toxic constituent of Neotropical frogs, Dendrobates pumilio and D. auratus, was synthesized by stereoselective methods. The starting materials chosen for the present synthesis of the base (1) are cis-tetrahydroindanone (12), and new 1,3-bis(tri-methylsiloxy)-1,3-dienes (8) and (9). The Beckmann rearrangement of the oxime (13) afforded the quinolone (14), which was derived into the N-benzyl compound (15). Successive treatments of (15) with MCPBA, 48% aq. HBr, CrO_3-H_2SO_4, and Li_2CO_3-LiBr gave the enone (19). Stereoselective conjugate addition of LiCuMe_2 to (19) yielded the N-benzyl keto-lactam (11). The Diels-Alder reaction of cyclic diene (8) with acrylonitrile, followed by 10% aq. HCl treatment gave the keto-nitrile (26). Successive treatments of (26) with C_5H_5NHBr_3, NaBH_4, Zn-AcOH, and 15% HClO_4-AcOH gave the keto-lactam (10) as a sole product. Another synthetic route to the keto-lactam (10) was as follows. Reaction of the acyclic diene (9) with ethyl crotonate yielded the adduct (32), which was derived into the ketal-ester(33). Treatment of (33) successively with LiAlH_4, n-BuLi-TsCl, CuCH_2CN, aq. H_2O_2-NaOH, dil. HCl, and NaOMe-MeOH afforded the keto-lactam (10). The keto-lactam (10) and N-benzyl keto-lactam (11) were derived into the lactam (7). Reaction of (7) with P_2S_5 gave the thiolactam (41), and subsequent treatment of (41) with bromoacetone afforded the thiazole (42), which was derived into dl-pumiliotoxin C in five steps. Alternatively, heating of N-butyryl compound (48), which was prepared from (7), with CaO afforded the imine (49). Catalytic hydrogenation of (49) gave dl-pumiliotoxin C as a single product.

• 天然有機化合物討論会の論文
• 1976-09-20

著者

• 田中 圭

  Faculty Of Pharmaceutical Sciences Kyoto University

• 森 裕二

  Faculty Of Pharmaceutical Sciences Kyoto University

• 田中 圭

  静岡県大 薬

• 井深 俊郎

  Faculty Of Pharmaceutical Sciences Kyoto University

• 真崎 規夫

  京大薬

• 森 裕二

  京大・薬

• 佐治 幾太郎

  京大・薬

• 田中 圭

  京大・薬

• 真崎 規夫

  京大・薬

• 井深 俊郎

  京大・薬

• 犬伏 康夫

  京大・薬

• 犬伏 康夫

  Faculty Of Pharmaceutical Sciences Kyoto University

• 真崎 規夫

  阪大理

• 田中 圭

  京都大学薬学部

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