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1993 Fiscal Year Final Research Report Summary

Asymmetric Synthesis Using Chiral Lewis Base

Research Project

Project/Area Number 04557097
Research Category

Grant-in-Aid for Developmental Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field Chemical pharmacy
Research InstitutionOsaka University

Principal Investigator

TOMIOKA Kiyoshi  Osaka University The Institute of Scientific and Industrial Research Professor, 産業科学研究所, 教授 (50114575)

Co-Investigator(Kenkyū-buntansha) INOUE Isao  Tanabe Seiyaku Ltd.Researcher, 製薬技術センター, 研究員
Project Period (FY) 1992 – 1993
KeywordsAsymmetric synthesis / Chiral catalyst / Organolithium / Amino ether / Chiral ether / beta-Lactam / Amines / Catalytic reaction
Research Abstract

Chiral Lewis base coordinates to metallic center of metallic reagents and activates the reagent. Consequently, it is highly probable that stereochemical control of the reaction would be achieved by coordination of the chiral Lewis base to metal. However, the use of chiral Lewis base in the reaction is quite rare in the modern synthetic chemistry. This is clearly contrasted to the familiar use of chiral Lewis acid as activator as well as stereoconytoller.
In the present research we focused on design, synthesis, and application of chiral Lewis base into asymmetric synthesis. Moreover, we applied the chiral Lewis base as a chiral catalyst in the reaction which can produce optically active compounds more than the equivalence of the chiral catalyst.
As a result of the studies we developed quite promising reactions as shown below.
1. Asymmetric synthesis of beta-lactam of more than 90% ee by the reaction of lithium ester enolate with imine in the presence of chiral amino ether catalyst.
2. Catalytic asymmetric synthesis of highly optically active beta-lactam using catalytic amount of chiral amino ether.
3. Catalytic asymmetric synthesis of amines of more than 90% ee by the reaction of organolithium with imines.
These promising results may open a new world of synthetic organic chemistry and its application to the industrial production.

  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] K.Tomioka et al: "Asymmetric Addition of Aryllithiums to Naphthalene BHA-Esters Catalyzed by a Chiral Ligand" Tetrahedron Letters. 34. 681-682 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Ando et al: "Asymmetric Alkylation of α-alkyl β-Keto Esters to α,α-Alkyl β-Keto Esters Having(R)-or(S)-Chiral Quaternary Center Depending on the Solvent System" Tetrahedron. 49. 1579-1588 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Tomioka: "Controle of Reaction and Stereochemistry" Farumasia. 29. 168-170 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Kanai et al.: "Solvent Effect and NMR Behaviour in a Chiral Amidophosphine Mediated Reaction of Organocuprate with Chalcone" J.Chem.Soc.,Chem.Commun.16. 1248-1249 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] I.Inoue et al.: "Steric Tuning in Chiral Ligand-Catalyzed Enantioselective Alkylation of Imines" Tetrahedron:Asymmetry. 4. 1603-1606 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Aoki et al.: "Reinvestigation of Optical Purities of Optically Active Trimethylsilil Enol Ethers of 4-Substituted Cyclohexanones" Chem.Pharm.Bull.41. 994-996 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 富岡 清、他3名: "有機化学実験ガイド" 廣川書店, 155 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Tomioka, M.Shindo K.Koga.: "Asymmetric Addition of Aryllithiums to Naphthalene BHA-Esters Catalyzed by a Chiral Ligand." Tetrahedron Letters. 34. 681-682 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Ando, Y.Takemasa, K.Tomioka, K.Koga.: "Asymmetric Alkylation of alpha-alkyl beta-Keto Esters to alpha, alpha-Alkyl beta-Keto Esters Having (R)-or (S)-Chiral Quaternary Center Depending on the Solvent System." Tetrahedron. 49. 1579-1588 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Tomioka.: "Controle of Reaction and Stereochemistry." Farumasia. 29. 168-170 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Kanai, K.Koga, K.Tomioka.: "Solvent Effect and NMR Behavior in a Chiral Amidophosphine Mediated Reaction of Organocuprate with Chalcone." J.Chem.Soc.Chem.Commun.1248-1249 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] I.Inoue, M.Shindo, K.Koga, K.Tomioka.: "Steric Tuning in Chiral Ligand Mediated Enantioselective Alkylation of Imines." Tetrahedron : Asymmetry. 4. 1603-1606 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Aoki, M.Nakajima, K.Tomioka, K.Koga.: "Reinvestigation of Optical Purities of Optically Active Trimethylsilyl Enol Ethers of 4-Substituted Cyclohexanones." Chem.Pharm.Bull.41. 994-996 (1993)

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

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Published: 1995-03-27  

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