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2000 Fiscal Year Final Research Report Summary

Synthetic Studies on Ring-Fused Macrocyclic Terpenoids

Research Project

Project/Area Number 11672132
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionTokushima Bunri University

Principal Investigator

KODAMA Mitsuaki  Tokushima Bunri University, Faculty of Pharmaceutical Sciences, Professor, 薬学部, 教授 (30004378)

Co-Investigator(Kenkyū-buntansha) HIOKI Hideaki  Tokushima Bunri University Faculty of Pharmaceutical Sciences, Associate professor, 薬学部, 助教授 (00208737)
Project Period (FY) 1999 – 2000
KeywordsBaker's yeast reduction / Trinervitane diterpene / (R)-4-methyl-Hajos-Parrish ketone / Glabrescol / Asymmetric total synthesis / Stereostructure revision
Research Abstract

This project aimed to synthesize novel Terpenoids having ring-fused macrocyclic skeleton, especially trinervitane diterpenoids with tricyclo[7.2.0^<1.16>] hexadecane carbocycle.
1. By applying kinetic resolution of (±)-4-methyl-Hajos-Parrish ketone using baker's yeast reduction, optically pure (R)-2,6-dimethylbicyclo[4.3.0]nona-l-ene-3,7-dione was obtained in good yield. By controlling the reaction time, it was possible to obtain the enantiomer in high optical purity.
2. Synthesis of trinervitane diterpene was examined. Starting from (R)-2,6-dimethylbicyclo[4.3.0]nona-l-ene-3,7-dione described above, various compounds with requisite side chains and oxygen functionarities were prepared. However, attempted formation of the third 11-menbered ring was unsuccessful in almost cases. The desired tricyclic compound was oobtained only by the intramolecular alkylation of a-sulfenyl anion in low yield.
3. Stereoselective synthesis of glabrescol, a novel mneso-type triterpene with five continuously linked tetrahydrofuran rings, was investigated. By applying baker' yeast reduction, asymmetric epoxidation, and asymmetric dihydroxylation as chilarity induction method, a compound having the structure reported for glabrescol was synthesized. But the spectral data were not identical to those of the natural product. Comparison of NMR spectra of Natural and synthetic compounds suggested that the stereochemistry around the central part of molecule is different. However, synthesized meso-compound with different configuration at the central THF ring was not identical to the natural product again. Thus, we could point out that the reported structure of glabrescol is incorrect. But, we could not propose the correct structure.

  • Research Products

    (6 results)

All Other

All Publications (6 results)

  • [Publications] 日置,橋本,児玉: "Efficient kinetic resolution of (±)-4-methyl-Hajos-Parrish ketone by baker's yeast reduction"Tetrahedrom : Asymmetry. 11. 829-834 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 日置,金原,大西,梅森,坂井,吉尾,松下,児玉: "What is the structure of Glabrescol ? Stereoselective Synthesis of Reported Glabrescol"Angew.Chem.Int.Ed.. 39(14). 2552-2554 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 福山,八十,森,高橋,三並,児玉: "Total Synthesis of Plagiochins A and D, Macrocyclic Bis (bibenzyls), by Pd (0) Catalyzed Intramolecular Still-Kelly Reaction"Heterocycles. 54(1). 259-274 (2001)

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      「研究成果報告書概要(和文)」より
  • [Publications] 日置,大井,濱野,三村,吉尾,児玉,太田,楊井,池上: "Enantioselective Total synthesis and absolute stereostructure of hippospongic acid A"Tetrahedron. 57(7). 1235-1246 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 児玉,日置,吉尾: "特異な構造や生物活性を有するテルペノイドの不斉全合成"有合化. 58(12). 1167-4630 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 伊東〓,児玉三明 共訳: "マクマリー有機化学概説 第4版"東京化学同人. 621 (2000)

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      「研究成果報告書概要(和文)」より

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Published: 2002-03-26  

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