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Enantioselective Synthetic Reactions using Chiral Lithium Amide Bases

Research Project

Project/Area Number 03403023
Research Category

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

Allocation TypeSingle-year Grants
Research Field Chemical pharmacy
Research InstitutionUniversity of Tokyo

Principal Investigator

KOGA Kenji  Faculty of Pharmaceutical Sciences profassor, 薬学部, 教授 (10012600)

Co-Investigator(Kenkyū-buntansha) NAKAJIMA Makoto  University of Tokyo, Faculty of Pharmaceutical Sciences assistant, 薬学部, 助手 (50207792)
KAWASAKI Hisashi  University of Tokyo, Faculty of Pharmaceutical Sciences assistant, 薬学部, 助手 (10186083)
新藤 充  東京大学, 薬学部, 助手 (40226345)
富岡 清  東京大学, 薬学部, 助教授 (50114575)
Project Period (FY) 1991 – 1993
Project Status Completed (Fiscal Year 1993)
Budget Amount *help
¥32,800,000 (Direct Cost: ¥32,800,000)
Fiscal Year 1993: ¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 1992: ¥7,600,000 (Direct Cost: ¥7,600,000)
Fiscal Year 1991: ¥21,800,000 (Direct Cost: ¥21,800,000)
KeywordsAsymmetric deprotonation / Asymmetricalkylation / Chiral lithium amide / Asymmetric protonation / Asymmetric catalytic reaction / Enantioselective reaction / Ligand exchange / Multinuclear NMR / キラル塩基 / 不斉合成 / 不斉アルドール反応 / 不斉プロント化 / メカニズム / リチウムアミド / X線結晶解析 / ^6LiNMR / ^<15>NNMR
Research Abstract

Studies using deuterated cyclohexanone derivatives determined the protons that are selectively deprotonated in the asymmetric deprotonation reactions
The stereochemistry of the asymmetric alpha-alkylation of cyclic ketones was clarified on the basis of the reactions with 4-substituted cyclohexanones
Asymmetric protonation of achiral enolates was achieved, based on which the method to convert racemic ketones into optically active ones was established. Studiesusing deuterated compounds clarified that this protonation proceeded through protonation of chiral amines
The solution structures of three chiral lithium amides were determined by ^6Li and ^<15>N-NMR spectroscopy, and their crystal structures were determined by X-ray analysis. The solution structure (agregation state) was able to be controlled by strong external ligands. The relationship between these results and the actual reactions was clarified.
The asymmetric deprotonation reactions described above were extended to catalytic asymmetric reactions, the mechanism of which was proposed
Catalytic asymmetric alkylation was successfully achieved with high efficiency. The mechanistic study is in progress.
Asymmetric aldol and Darzens reactions using chiral bases were achieved

Report

(4 results)
  • 1993 Annual Research Report   Final Research Report Summary
  • 1992 Annual Research Report
  • 1991 Annual Research Report
  • Research Products

    (20 results)

All Other

All Publications (20 results)

  • [Publications] Daisaku Sato: "Crystallographic and Li-6 and N-15 NMR Studies of a Chiral Bidentate Lithium Amide." J.Am.Chem.Soc.114. 761-763 (1992)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Tatsuro Yasukata: "Enantioselective Protonation of Achiral Lithium Enolates Using a Chiral Amine in the Presence of Lithium Bromide." Tetrahedron:Asymmetry. 4. 35-38 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Yoshihiro hasegawa: "Control of Diastereoselectivity in the Alkylation of Chiral Lithium Enolates Mediated by a Chiral Secondary Amine Ligand." Tetrahedron Letters. 34. 1963-1966 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kazumasa Aoki: "Reinvestigation on the 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(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Masao Sobukawa: "Determination of the Protons Eliminated in the Regioselective Deprotonation of Some Optically Active 3-Keto Steroids." Tetrahedron Letters. 34. 1501-1504 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kazumasa Aoki: "Enantioselective Deprotonation of 4-Substituted Cyclohexanones by Chiral Lithium Amides Having a Fluorine-containing Group." Tetrahedron Letters. 34. 1505-1508 (1993)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Daisaku Sato: "Crystallographic and Li-6 and N-15 NMR Studies of a Chiral Bidentate Lithium Amide" J.Am. Chem. Soc. 114. 761-763 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Tatsuro Yasukata: "Enantioslelctive Protonation of Achiral Lithium Enolates Using a Chiral Amine in the Presence of Lithium Bromide" Tetrahedron Asymmetry. 4. 35-38 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Yoshihiro Hasegawa: "Control of Diastereoselectivity in the Alkylation of Chiral Lithium Enolates Mediated by a Chiral Secondary Amine Ligand" Tetrahedron Letters. 34. 1963-1966 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kazumasa Aoki: "Reinvestigation on the 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
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Masao Sobukawa: "Determination of the Protons Eliminated in the Regioselective Deprotonation of Some Optically Active 3-Keto Steroids" Tethahedron Letters. 34. 1501-1504 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Kazumasa Aoki: "Enantioselective Deprotonation of 4-Substituted Cyclohexanones by Chiral Lithium Amides Having a Fluorine-containing Group" Tetrahedron Letters. 34. 1505-1508 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1993 Final Research Report Summary
  • [Publications] Daisaku Sato: "Crystallographic and Li-6 and N-15 NMR Studies of a Chiral Bidentate Lithium Amide." J.Am.Chem.Soc.114. 761-763 (1992)

    • Related Report
      1993 Annual Research Report
  • [Publications] Tatsuro Yasukata: "Enantioselective Protonation of Achiral Lithium Enolates Using a Chiral Amine in the Presence of Lithium Bromide." Tetrahedron:Asymmetry. 4. 35-38 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Yoshihiro hasegawa: "Control of Diastereoselectivity in the Alkylation of Chiral Lithium Enolates Mediated by a Chiral Secondary Amine Ligand." Tetrahedron Letters. 34. 1963-1966 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Kazumasa Aoki: "Reinvestigation on the Optical Purities of Optically Active Trimethylsilyl Enol Ethers of 4-Substituted Cyclohexanones." Chem.Pharm.Bull.41. 994-996 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Masao Sobukawa: "Determination of the Protons Eliminated in the Regioselective Deprotonation of Some Optically Active 3-Keto Steroids." Tetrahedron Letters. 34. 1501-1504 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Kazumasa Aoki: "Enantioselective Deprotonation of 4-Substituted Cyclohexanones by Chiral Lithium Amides Having a Fluorine-containing Group." Tetrahedron Letters. 34. 1505-1508 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] T.Yasukata: "Enantioselective Protonaeion of Achiral Lithium Enolates Using a chiral Amine in the Presence of Lithiam Bromide" Tetrahedron:Asymmetry. 4. 35-38 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] D.Sato: Journal of American Chemical Society. 114. 761-763 (1992)

    • Related Report
      1991 Annual Research Report

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Published: 1991-04-01   Modified: 2016-04-21  

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