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1996 Fiscal Year Final Research Report Summary

Utilization of Meso Substrates by Catalytic Asymmetrization Reaction

Research Project

Project/Area Number 07672255
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionTOHOKU UNIVERSITY

Principal Investigator

KOU Hiroya  Tohoku University Fuculty of Pharmaceutical Sciencies Associated Professor, 薬学部, 助教授 (70192721)

Project Period (FY) 1995 – 1996
Keywordsmeso diol / asymmetric isomerization reaction / chiral BINAP / cationic rhodium complex / 4-hydroxy-2-cyclochexenone / tropane alkalid / physoperuvine / meso endo diol bis-silyl ether
Research Abstract

The asymmetric olefin migration reaction catalyzed by the cationic Rh-complex ligated with chiral BINAP had been investigated. At the beginning, the diol and the analogus which were easily prepared from the cyclopentadiene and benzoquione were used as the substrates.
The following facts were discovered during investigation :
1) The optical yield was 43%, when the diol was used as the substrate.
2) The almost perfect results were obtained, when the bis-siltl ethers were used.
3) The optical yield does not related to the bulkiness of the silyl functional group.
4) The bis-alkyl ethers did not bring about good enantiomeric excess.
5) The bis-ester did not work at all.
6) The course of the olefin migration was inversely between the diol and the bis-silyl ether.
Next, this methodology was further applied to the 7-membered meso-ene-diol. The first enantiomeric synthesis of the tropane alkaloid, physoveruvine was achieved from the isomerized product.

  • Research Products

    (20 results)

All Other

All Publications (20 results)

  • [Publications] Kou Hiroya: "Asymmetrization of meso 1,4-Enediol Ethers by Isomerization with a Chiral binap-Rh^I Catalyst" Angew.Chem.Int.Ed.Engl.34. 2287-2289 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kou Hiroya: "Catalytic Asymmetrization of meso-3,7-Bis-siloxycycloheptene by Chiral Rhdium(1)-binap[2,2′-bis(diphenylphsphino)-1,1′-binaphthyl]Catalyst:the Enantiocontrolled Asymmetric Synthesis of(-)-(S)-Physoperuvine" J.Chem.Soc.,Chem.Commun.2205-2206 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takashi Watanabe: "Lipase-Mediated Route to Diastereo-Pure Tranexamic Acid" Chem.Pharm.Bull.43. 529-531 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuya Hashimura: "A Stereocontrolled Route to Both Enantiomers of the Necine Base Dihydro-heliotridane via Inthamolecular 1,3-Dipolar Addition Usingthe Same Chiral Precursor" J.Chem.Soc.,Chem.Commun.2291-2292 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kou Hiroya: "Lipase-Mediated Kinetic Separation of a Diastereomeric Mixture of 4-tert-Butylcyclohexanemethanol" Synthesis. 379-381 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kou Hiroya: "Enantio-and Diastereocontrolled Synthesis of Epibatidine Analogues" Chem.Pharm.Bull.43. 901-903 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kou Hiroya: "An Expeditious Route to 3-Formylfuran" SYNLETT. 175-176 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takahiro Yamane: "An Enantioconvergent Construction of the Key Intermediate of(+)Vincamine" Heterocycles. 42. 65-70 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takashi Kamikubo: "Stereo-and Enantio-Controlled Synthesis of two Naturally Occurring Polyoxygenated Cyclohexene-methaolds,(+)-Epiepoxydon and(-)-Phyllostine,via Catalytic Asymmetrization of a Meso Substrate" Tetrahedron Lett.37. 499-502 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Masanori Saito: "The First Enantiocontrolled Syntheses of(+)-Uleine and(+)-Dasycarpidone" Chem.Commun.(印刷中). (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kou Hiroya: "Asymmetrization of meso 1,4-Enediol Ethers by Isomerization with a Chiral binap-Rh^I Catalyst." Angew. Chem. Int. Ed. Engl.34. 2287-2289 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kou Hiroya: "Catalytic Asymmetrization of meso-3,7-Bis-siloxy-cyxloheptene by Chiral Rhdium (I)-binap [2,2'-bis (diphenylphsphino)-1,1'-binaphthyl] Catalyst : the Enantiocontrolled Asymmetric Synthesis of (-)-(S)-Physoperuvine" J.Chem. Soc., Chem. Commun.2205-2206 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Takashi Watanabe: "LiPase-Mediated Route to Diastereo-Pure Tranexamic Acid" Chem. Pharm. Bull.43. 529-531 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuya Hashimura: "A Stereocontrolled Route to Both Enantiomers of the NecineBase Dihydroheliotridane via Intramolecular 1,3-Dipolar Addition Using the Same Chiral Precursor" J.Chem. Soc., Chem.Commun.2291-2292 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kou Hiroya: "Lipase-Mediated Kinetic Separation of a Diatereomeric Mixture of 4-tert-Butylcyclochexanemethanol" Synthesis. 379-381 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kou Hiroya: "Enantio- and Diastereocontrolled Synthesis of Epibatidine Analogues" Chem. Pharm. Bull.43. 901-903 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kou Hiroya: "An Expeditious Route to 3-Formylfuran" SYNLETT. 175-176 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Takahiro Yamane: "An Enantioconvergent Construction of the Key Intermediate of (+)-Vincamine" Heterocycles. 42. 65-70 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Takashi Kamikubo: "Stereo- and Enantio-Controlled Synthesis of two Naturally Occurring Polyoxygenated Cyclohexebemethanols, (+)-Epiepoxydon and (-)-Phyllostine, via Catalytic Asymmetrization of a Meso Substrate" Tetrahedron Lett.37. 499-502 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Masanori Saito: "The First Enantiocontrolled Syntheses of (+)-Uleine and (+)-Dasycarpidone" Chem. Commun.(in press).

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1999-03-09  

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