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New Development of Asymmetric Olefination

Research Project

Project/Area Number 09672141
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionUniversity of Shizuoka (1998)
Kyoto University (1997)

Principal Investigator

TANAKA Kiyoshi  University of Shizuoka, Pharm.Sci.Professor, 薬学部, 教授 (50093266)

Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 1998: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1997: ¥2,400,000 (Direct Cost: ¥2,400,000)
KeywordsAsymmetric reaction / HWE reaction / Chiral phosphonate / Diketone / MO calculation / Axial chirality / Intramolecular reaction / Chiral allenes / 不斉オレフィン化 / H.W.E.反応 / フォスフォネート試薬 / 絶対構造 / 速度論的支配 / 軌道支配 / 面斉不斉
Research Abstract

The scientific research works of the asymmeric olefination, the research planning of which are described in the grant application form in detail, were performed and the following results are obtained.
1. A variety of diketonic substrates were applied to the asymmetric olefination utilizing the axially chiral phosphonate reagent of the HWE type, and the general effectiveness of the reagent was positively proven. Therein, the absolute stereostructure of the products was determined by chemical transformations as well as the X-ray crystal analyses.
2. The mechanistic aspects of the reaction was considered, where the kinetically controlled mechanism of the nucleophilic attack of the anion to the ketonic substrate as the rate determining step was proposed. The direction of the nucleophilic attack was estimated by using model experiments of thc Grignard reagents. From these model experiments and the calculation, it turned out that the direction was governed by the orbital control factors rather … More than the steric ones.
3. A practical and efficient synthetic method based on the C-C bond formation was developed by using the BHT esters as the ketene equivalent. The new reaction system afforded the higher chemical and optical yield than the previously known method. In this study, it was shown that even the simple phenolic esters can be the precursor for the ketenes and gave the corresponding optically active allenic esters in satisfactory chemical and optical yield.
4. The o-symmetrical diketones bearing the optically active phosphonate moiety were designed and prepared and intramolecular asymmetric HWE reaction based on the discrimination of the carbonyls was investigated. The optically active ring system having quaternary carbon and tetra-substituted olefinic moiety was successfully constructed in satisfactory chemical and optical yield. The absolute stereostructure of some of the products was unambiguously elucidated by the X-ray crystal analysis.
5. The symmetrical metal (Fe and Cr) complexes of diene and arenes were applied as the substrates to the asymmetric olefination, and the corresponding olefinic products of the planar chirality was obtained in satisfactory chemical and optical yield.
6. The preliminary experiments of the kinetic resolution of the racemic ketones was investigated. In the case of some amino acid derivatives, the high optical yield of the olefinic products was achieved and these extensive investigations are in progress. Less

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • Research Products

    (15 results)

All Other

All Publications (15 results)

  • [Publications] 田中 圭 他: "Formation of Non-racemic E-and Z-Olefins Based on Discrimination of Enantiotopic Carbonyl Groups in α-Diketones by a Chiral Phosphonate Reagent" Tetrahedron Letters. 38. 8943-8946 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 田中 圭 他: "Use of 8, 8'-Dihydroxy-1, 1'-binaphthalene as a Chiral Auxiliary for Asymmetric Diels-Alder Cycloadditions" Tetrahedron : Asymmetry. 8. 3637-3645 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 田中 圭 他: "Diastereoselective Reactions of 1, 1'-binaphthyl Ester Enolates with Carbonyl Electrophiles" J.Chem.Soc., Perkin Trans.1. 185-192 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 田中 圭 他: "光学活性リン試薬を用いる不斉オレフィン化 Asymmetric Olefimation Using Optically Active Phosphonate Reagents" 有機合成化学協会誌. 56. 521-532 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Kiyoshi Tanaka, Toshiyuki Watanabe, Yoshihisa Ohta, and Kaoru Fuji: "Formation of Non-racemic E-and Z-Olefins Based on Discrimination of Enantiotopic Carbonyl Groups in alpha-Diketones by a Chiral Phosphonate Reagent." Tetrahedron Letters. 38-52. 8943-8946 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Kiyoshi Tanaka, Naoyuki Asakawa, Mohammad Nuruzzaman, and Kaoru Fuji: "Use of 8, 8'-dihydroxy-1, 1'-binaphthalene as a chiral auxiliary for asymmetric Diels-Alder cycloadditions" Tetrahedron : Asymmetry. 8-21. 3637-3645 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Mija Ahn, Kiyoshi Tanaka, and Kaoru Fuji: "Diastereoselective reactions of 1, 1'-binaphthyl ester enolates with carbonyl electrophiles" J.Chem.Soc., Perkin Trans.1. 1. 185-192 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Kiyoshi Tanaka, and Kaoru Fuji: "Asymmetric Olefination Using Optically Active Phosphonate Reagents" J.Synth.Org.Chem.Jp.56-6. 521-531 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 田中 圭 他: "Formation of Non-racemic E-and Z-Olefins Based on Discrimination of Enantiotopic Carbonyl Groups in α-Diketones by a Chiral Phosphonate Reagent" Tetrahedron Letters. 38.52. 8943-8946 (1997)

    • Related Report
      1998 Annual Research Report
  • [Publications] 田中 圭 他: "Use of 8,8'-Dihydroxy-1,1'-binaphthalene as a Chiral Auxiliary for Asymmetric Diels-Alder Cycloadditions" Tetrahedron: Asymmetry. 8・21. 3637-3645 (1997)

    • Related Report
      1998 Annual Research Report
  • [Publications] 田中 圭 他: "Dlastereoselective Reactions of 1,1'-binaphthyl Ester Enolates with Carbonyl" J.Chem.Soc.,Perkin Trans.1. .1. 185-192 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 田中 圭 他: "光学活性リン試薬を用いる不斉オレフィン化 Asymmetric Olefimation Using Optically Active Phosphonate Reagents" 有機合成化学協会誌. 56・6. 521-532 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 田中 圭 他: "Formation of Non-racemic E-and Z-Olefins Based on Discrimination of Enantiotopic Carbonyl Groups in α-Diketones by a Chiral Phosphonate Reagent." Tetrahedron Letters. 38・52. 8943-8946 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 田中 圭 他: "Diastereoselective Reactions of 1,1'-Binaphthyl Ester Enolates with Carbonyl Electrophole" J.Chem.Soc.,Perkin 1. 1. 185-192 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] 田中 圭 他: "光学活性リン試薬を用いる不斉オレフィン化" 有機合成化学協会誌. 56・6(印刷中). (1998)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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