41 3-Spirooxindoleの誘導体の合成研究 : dl-Formosanine,dl-Isoformosanine,dl-Mitraphylline,dl-Isomitraphyllineの全合成

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• Formosanine(uncarine-B) and isoformosanine(uncarine-A) were isolated from Uncaria kawakamii and Ourouparia formosana, and mitraphylline and isomitraphylline are the alkaloids of Mitragina species. The structures of these alkaloids are delineated in Fig. I, in which their relationship as stereoisomers is shown by their ready interconversion and equilibration with acid or base. The total synthesis of formosanine and isoformosanine has been achieved by Winterfeldt by an oxidative conversion of the indole to the oxindole at the final step. The new synthesis of the entitled alkaloids through ten steps starting from the condensation of 2-hydroxytryptamine with the aldehyde(3) is reported with an interest in the proposal on the biosynthesis of indole alkaloids made by Scott. The first condensation product(5) was submitted to the Michael addition with methyl vinyl ketone, followed by acid treatment to give the α,β-unsaturated ketones as two stereoisomers(8a,b). The isomer(8a) was condensed with methyl malonate with sodium methoxide(0.5 mol.eq.) to yield the ester(11a), which was hydrogenated with Adams' catalyst to 12a. The compound(12a) was treated with dil. sulfuric acid to give the lactones(13a,b) as two spiro-isomers, an isomer(13b) of which in turn, was heated with the aminal ester in DMF for 2 hrs, then stirred with 5% MeOH-HCl overnight, refluxed with aqueous dioxane for 20 hrs, and heated with PPA at 70°for 2 hrs to afford dl-isoformosanine(1a) in 19% yield and dl-formosanine(1b) in 35% yield from 13b. Similarly, the isomer(15b) which was obtained from 11a by reduction with NaBH_4 and hydrolysis with acid, gave dl-isomitraphylline(2a) and dl-mitraphylline(2b) in 16% and 27% yields, respectively. The synthetic racemic alkaloids were identified with the natural products by direct comparisons of their i.r. spectra in chloroform solutions in addition to the other spectral data.

• 天然有機化合物討論会の論文
• 1973-10-01

著者

• 伴 義雄

  北大・薬

• 伴 義雄

  東邦大・薬

• 伴 義雄

  Faculty Of Pharmaceutical Sciences Hokkaido University

• 大石 武

  北大・薬:(現)理化学研究所

• 多賀 尚正

  Faculty Of Pharmaceutical Sciences Hokkaido University

• 多賀 尚正

  北大・薬

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