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The Establishment and Application of Simple Catalytic Preparation of High Optical Active Chiral Compounds

Research Project

Project/Area Number 10554037
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field Organic chemistry
Research InstitutionYamaguchi University

Principal Investigator

OGUNI Nobuki  Department of Chemistry and Earth Science, Yamaguchi University Professor of Chemistry,, 理学部, 教授 (60028165)

Co-Investigator(Kenkyū-buntansha) HARADA Katsumasa  Ube Chemical Ind. Ube Institute, Research Manager,, 有機合成部長
Project Period (FY) 1998 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥11,400,000 (Direct Cost: ¥11,400,000)
Fiscal Year 1999: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1998: ¥10,000,000 (Direct Cost: ¥10,000,000)
KeywordsAldehyde / Diketene / Enantioselective reaction / Chiral schiff base / Titanium complex / Cholesterol / Optical active product / 光学活性化合物 / キラルなシッフ塩基 / チタン触媒 / 対称エポキシド / 不斉開環アルキル化
Research Abstract

The reaction of aldehydes with diketene is known to give 5-hdroxy-3-ketoesters by Lewis acid catalyst like TiClィイD24ィエD2. But the products in this reaction are racemic mixture and the reaction of cinnamic aldehyde with diketene did not give addition product. The author obtained the products in high yield using Ti(OiPr)ィイD24ィエD2 as catalyst. Also we found the above enantioselective reaction catalyzed by chiral schiff base-titanium complexes which were very effective for the asymmetric reaction of aldehydes with trimethylsilyl cyanide. In this reaction the some optically active product become precursor of synthetic drugs, particularly active for lowering cholesterol. The results of optimization research afforded the reaction conditions giving 90% ee's product in good yield. Also in the use of 20 mol% of the chiral catalist gave the product in good enantio-selectivity only in use of an equimolar amount of Ti(OiPr)ィイD24ィエD2. The recovery of the chiral catalyst was accomplished by cationic resins such as Dowex which was revailed by the research in Ube Chemical Institute.

Report

(3 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • Research Products

    (28 results)

All Other

All Publications (28 results)

  • [Publications] M.Hayashi,K.Ono,H.Hishimi,N.Oguni,: "Asymmetric ring opening reaction of symmetrical N-Acylaziridines with thiols catalyzed by chiral dialkyl tertrate-diethylzinc complexes"Tetrahedron. 52. 7817-7832 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 小国信樹: "対称化合物の非対称化操作一特に不斉触媒による環状化合物の開環"有機合成化学協会誌. 54. 829-835 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N,Oguni.K,Tanaka,H,Tshida,: "Catalytic enantiosalective reaction of diketene with aldehydes catalyzedby Chiral schiff base-titanium alkoxide complexes"Synlett. 601-602 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N.Oguni,Y.Miyagi,K.Itoh,: "Highly enantioselective arylation of symmerical eposides with phenyllithium promoted by chiral schiff bases and salens"Tetrahedron Letters,. 39. 9023-9026 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N.Oguni,N.Satoh.: "Highly enantioselective methylation of 3-trimethylsilylpropanal with dimathylzinc catalyzed by chiral schiff base-titanium complexes"Terahedron Letters,. 41(印刷中). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N.Oguni: "Metal Catalyzed Addition of Cyanides to Aldehydos.in "Transition metal for Oganic Synthesis"Ed.M.Beller,C.Bolm."Wiley-VCH. (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N.Oguni: "Zinc(II) Reagents in "Lewis Acid Reagents.A Practical Approach"Ed.H.Yamamoto"Oxford University Press,. 23 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] OGUNI, N et al: "Asymmetric ring-opening reaction of symmetrical N-acylaziridines with thiols catalyzed by chiral dialkyl tartarate-diethylzinc complexes"Tetrahedron. 52. 7817-7832 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] OGUNI, N: "Asymmetric Desymmetrization of symmetrical organic compounds"Journal of Synthetic Organic Chemistry. 54. 829-835 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] OGUNI, N et al: "Catalytic enantioselective reaction of diketene with aldehydes catalyzed by chiral schiff base-titanium alkoxide complexes"Synlett. 601-602 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] OGUNI, N et al: "Highly enantioselective arylation of symmetrical epoxides with phenyl lithium promoted by chiral schiff base and salens"Tetrahedron Letters. 39. 9023-9026 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] OGUNI, N: "Highly enantioselective methylation of 3-trimethylsilylpropinal with dimethylzinc catalyzinc catalyzed by chiral schiff base-titanium complexes"Tetrahedron Letters. 41(in press). (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] OGUNI, N: "Metal Catalyzed Addition of Cyanide to Aldehydes "Transition Metal for Organic Synthesis" Ed. by M. Beller and C. Bolm."Wiley-VCH. 325-330 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] OGUNI, N: "Zinc(II) Reagents. "Lewis Acid Reagents" Ed. by YAMAMOTO, H"Oxford. 77-88 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] M.Hayashi,K,Ono,H.hoshimi,N.Oguni: "Asymmetric ring opening reaction of symmetrical N-Acylaziridines with thiols catalyzed by chiral dialkyl tartrate-diethylzinc complexes."Tetrahedron. 52. 7817-7832 (1996)

    • Related Report
      1999 Annual Research Report
  • [Publications] 小国信樹: "対称化合物の非対称化操作-特に不斉触媒による環状化合物の開環"有機合成化学協会誌. 54. 829-835 (1996)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Oguni,K,Tanaka,H.Ishida,: "Catalytic enatioselective reaction of diketene with aldehydes catalyzed by chiral schiff base-titanium alkoxide complexes."Synlett. 601-602 (1998)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Oguni,Y.Miyagi,K.Itoh,: "Highly enantioselective arylation of symmetrical epoxides with phenyllithium promoted by chiral schiff bases and salens."Tetrahedron Letters,. 39. 9023-9026 (1998)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Oguni,N.Satoh,: "Highly enatioselective methylation of 3-trimethylsilypropanal with dimethylzinc catalyzed by chiral schiff base-titanium complexes."Tetrahedron Letters,. 41(印刷中). (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Oguni: "Metal Catalyzed Addition of Cyanides to Aldehydes.in "Transition metal for Organic Synthesis" Ed.M.Beller,C.Bolm"Wiley-VCH. 6 (1998)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Oguni: "Zinc(II) Reagents in "Lewis Acid Reagents.A Practical Approach" Ed. H. Yamamoto."Oxford University Press,. 23 (1998)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Hayashi,K.Ono,H.Hoshimi,N.Oguni: "Asymmetric ring opening reaction of symmetrical N-Acylaziridines with thiols catalyzed by chiral dialkyl tartrate-diethylzinc complexes." Tetrahedron. 52. 7817-7832 (1996)

    • Related Report
      1998 Annual Research Report
  • [Publications] 小国信樹: "対称化合物の非対称化操作ー特に不斉触媒による環状化合物の開環." 有機合成化学協会誌. 54. 829-835 (1996)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Oguni,K.Tanaka,H.Ishida,: "Catalytic enantioselective reaction of diketene with aldehydes catalyzed by chiral schiff base-titanium alkoxide complexes." Synlett. -. 601-602 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Oguni,Y.Miyagi,K.Itoh,: "Highly enantioselective arylation of symmetrical epoxides with phenyllithium promoted by chiral schiff bases and salens." Tetrahedron Letters,. 39. 9023-9026 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Oguni,N.Satoh,: "Highly enantioselective methylation of 3-trimethylsilylpropanal with dimethylzinc catalyzed by chiral schiff base-titanium complexes." Tetrahedron Letters,. 40(印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Oguni: "Metal Catalyzed Addition of Cyanides to Aldehydes.in “Transition metal for Organic Synthesis" Ed.M.Beller,C.Bolm" Wiley-VCH, 6 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Oguni: "Zinc(II) Reagents.in “Lewis Acid Reagents.A Practical Approach" Ed.H.Yamamoto." Oxford University Press,23 (1998)

    • Related Report
      1998 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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