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1995 Fiscal Year Final Research Report Summary

Construction of Asymmetric Space and Catalytic Stereoselection with C_2-Symmetrical Molecules

Research Project

Project/Area Number 06640765
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field 物質変換
Research InstitutionShizuoka University

Principal Investigator

YODA Hidemi  Shizuoka University, Engineering, Associate Professor, 工学部, 助教授 (20201072)

Project Period (FY) 1994 – 1995
KeywordsBisoxazoline / Chiral Ligand / Metal Complex / Amino Acid / Tartaric Acid / C_2-Imide / Nucleophilic Addition / Deoxygenation
Research Abstract

1. According to my research scheme, asymmetric catalyst with the bisoxazoline ring system could be obtained from the coupling reaction of 2 equiv.of chiral amino alcohols with malononitrile-derived imidate and its activity as a chiral catalyst was investigated based on the alkylation of benzaldehyde with diethylzinc. Consequently, this reaction proceeded in about 40% ee.
2. Consecutive treatment of C_2-symmetrical imides elaborated from L-tartaric acid with Grignard reagent and NaBH_4 afforded separable diastereomixture of chiral amide alcohols in high selectivity. Using these amide alcohols as catalysts, asymmetric alkylation with diethylzinc was investigated and the results are as follows ;
(1) increasing a steric bulkiness of the N-substituent leads to an increase of the enantioselectivity.
(2) maximally the catalyst recycles 18.8 times.
(3) higher selectivity was obtained in the case of the catalyst with (4S)-configuration.
(4) to enhance the selectivity ether is preferable over toluene as a solvent.
Further, cyclic amides derived from D-arabinofuranose were also submitted to the same type of chiral catalytic reactions. It is interesting that no procedure for the asymmetric reactions with diethylzinc employing such as amide alcohols of cyclic amides as chiral catalysts has so far appeared.
3. In addition to these reactions, asymmetric total syntheses of antibiotics, (-)-anisomycin and (+)-preussin were accomplished employing stereoselective nucleophilic addition and asymmetric deoxygenation of the hydroxy lactam intermediate elaborated from the same starting material, arabinofuranose.13EA09 : In summary, two new types of chiral ligands were prepared and investigated based on their catalytic activity and two antibiotic natural products were synthesized.

  • Research Products

    (10 results)

All Other

All Publications (10 results)

  • [Publications] Hidemi Yoda: "Diastereo selective Reactions of Gngnard Reagents with Chiral Amino Lactols Deriued from L-Aspartic Acid" Tetrahedron:Asymmetry. 5. 169-172 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hidemi Yoda: "A Short Synthetic Approach to Enantio merically Pure(-)-Anisomycin" Heterocycles. 41. 2423-2426 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hidemi Yoda: "An Efficient Asymmetric Functionalization to Highly Substituted Pyrrolidines" Tetrahedron:Asymmetry. 6. 2669-2672 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hidemi Yoda: "A Novel Stereoselectiue Synthesis of Enantiomerically Pure Antifungal Agent,(+)-Preussin" Tetrahedron:Asymmetry. (in press).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 依田秀実: "キラル環境下での触媒的分子制御法の開発と生理活性体への合成的応用" 静岡大学工学振興基金助成研究報告. 1. 7-16 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hidemi Yoda: "Diastereoselective Reaction of Grignard Reagents with Chiral Amino Lactols Derived from L-Aspartic Acid" Tetrahedron : Asymmetry. 5. 169-172 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hidemi Yoda: "A Short Synthetic Approach to Enantiomerically Pure (-)-Anisomycin" Heterocyles. 41. 2423-2426 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hidemi Yoda: "An Efficient Asymmetric Functionalization to Highly Substituted Pyrrolidines" Tetrahedron : Asymmetry. 6. 2669-2672 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hidemi Yoda: "A Novel Stereoselective Synthesis of Enantiomerically Pure Antifungal Agent, (+)-Preussin" Tetrahedron : Asymmetry. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hidemi Yoda: "Development of Catalytic Molecular Control Methods under Chiral Conditions and Their Synthetic Application to Biomolecules" Report of Shizuoka University Fund for Engineering Research. 1. 7-16 (1995)

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

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Published: 1997-03-04  

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