36 3-Spirooxindole誘導体の合成研究 : (±)Rhynchophyllineおよび(±)Isorhynchophyllineの立体選択的合成

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概要

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• Rhynchophylline(I) and isorhynchophylline(II) are alkaloids of Uncaria rhyn-chophylla MIQ., the structures of which were established as I and II, respectively. Although the partial synthesis of rhynchophylline from dihydro-corynantheine and synthesis of (±)-rhynchophyllol and (±)-isorhynchophyllol were reported, the total synthesis of these alkaloids has not yet been described. We now report the stereoselective total synthesis of (±)-rhynchophylline and (±)-isorhynchophylline. A condensation of 2-hydroxytryptamine hydrochloride(IV) with morroniside(III), one of secoiridoid glucosides proved to be a precursor of indole alkaloids, was attempted to afford VI and the conversion of VI into oxindole alkaloids was tried, but this project has not yet been realized. Subsequently, ethyl sodium formyl acetate(XI) was used instead of hemiacetals like morroniside and tetrahydropyranol to condense with IV, namely, a mixture of XI and IV in the 1:1.8 molar ratio, was kept at 45-48°for two days to give exclusively XIII as an oil. The compound(XIII) was condensed with ethyl α-formyl butyrate to yield the enamine(XIV), which was submitted to hydrogenation with Adams' catalyst in acetic acid, yielding the diester(XV) as two isomers. The diester(XV) was refluxed with sodium hydride in toluene and the resulting ketoester was heated in hydrochloric acid at reflux to give the ketone(XVIa, b) in two isomeric forms. The ester(XVII) was obtained as a sole product from either isomer of XVI through the Wittig condensation with methyl diethyl-phosphonoacetate. The further conversion of XVII provided stereoselectively (±)-isorhynchophylline via XIXb and XX. The synthetic sample was identified with the natural alkaloid in respects of spectral and chromatographic properties. The synthetic (±)-isorhynchophylline was converted into (±)-rhynchophylline, which was also identified with the natural rhynchophylline by i.r.(CHCl_3) and mass spectra and the Rf values of t.l.c. The compound(XIII) should be also available as an important intermediate for the synthesis of other oxindole alkaloids including uncarine and mitraphylline, which is under investigation.

• 天然有機化合物討論会の論文
• 1972-10-01

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

• 瀬戸 正彦

  北大・薬

• 越後 康博

  北大・薬

• 瀬戸 正彦

  Faculty Of Pharmaceutical Sciences Hokkaido University:(present Addresses)organic Chemistry Research

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