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Development and Application of the Highly Efficient and Highly Stereoselective Synthetic Methods for Optically Active Cyelic Compounds by Asymmetric cycloaddition Reactions

Research Project

Project/Area Number 08640678
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKanazawa University

Principal Investigator

UKAJI Yutaka  Kanazawa University, Faculty of Sciences, Associate Professor, 理学部, 助教授 (80193853)

Project Period (FY) 1996 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1997: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1996: ¥1,600,000 (Direct Cost: ¥1,600,000)
Keywordsallylic alcohol / tartaric acid ester / optically active / 2-isoxazoline / nitrile oxide / nitrone / cyclopropane / cycloaddition reaction / 電子吸引基 / γ-アミノアルコール / β-ヒドロキシケトン / イソオキサゾリジン
Research Abstract

It is strongly required to develop a practical and efficient method for the construction of chiral molecules to explore new biologically active medicines and agricultural chemicals. It is obvious that the design of the specific chiral environment utililzing the chiral auxiliaries whose both enantiomers are easily available provides a useful way to prepare various optically active chemicals. Among such chiral auxiliaries, tartaric acid ester is one of the most promising and readily available candidates.
In this research, a new and novel chiral system possessing two metal centers utilizing tartaric acid esters was designed ; that is, if two reactants are bound to two different metal centers of the dialkoxide derived from tartaric acid ester, which might actually form the rigid 5/5-fused bicyclic dinucleating structure, they might be ideally oriented and/or activated by the metals and the following reaction might proceed in an enantioselective manner to afford the corresponding optically active products. According to this hypothesis, we could develop an asymmetric Simmons-Smith reaction, asymmetric 1,3-dipolar cycloaddition reactions of nitrile oxides and nitrones. Easy availability of (R,R)- and (S,S) -tartaric acid esters has now made it possible to prepare both enantiomers of the required chemicals by quite simple procedures.

Report

(3 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • Research Products

    (26 results)

All Other

All Publications (26 results)

  • [Publications] K.Inomata and Y.Ukaji: "Development of the Asymmetric Cycloaddition Reactions and AsymmetricNucleophilic Addition Reaction Utilizing Tartaric Acid Esters" J.Synth.Org.Chem.Jpn,. 56. 11-21 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Ukaji: "Design of the Chiral Reaction Field Utilizing Tartaric Acid Esters" Kagaku to Kogyo. 50. 167-170 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] A.Shibayama, T.Nakamura, T.Shintani, Y.Ukaji, H.Kinoshita, and K.Inomata et al: ""Syn-Effect" in the Desulfonylation Reaction of α,α-Dialkylated (E)-Allyic Sulfones" Bull.Chem.Soc.Jpn.70. 381-396 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Ukaji, K.Taniguchi, K.Sada, andK.Inomata: "Enantio-and DiastereoselectiveSynthesis of Isoxazolidines by Asymmetric 1,3-Dipolar Cycloaddition of Nitrones" Chem.Lett.547-548 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Ukaji, Y.Shimizu, Y.Kenmoku, A.Ahmed, and K.Inomata: "Catalytic Asymmetric Addition Reaction of Dialkylzinc to Nitrone Utilizing Tartaric Acid Ester as a Chiral Auxiliary" Chem.Lett.59-60 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] M.Shimizu, Y.Ukaji, and K.Inomata: "Catalytic Asymmetric 1,3-Dipolar Cycloaddition of Nitrile Oxide to an Achiral Allyl Alcohol Utilizing Diisopropyl Tartrate as a Chiral Auxiliary" Chem.Lett.455-456 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Ukaji, M.Miyamoto, M.Mikuni, S.Takeuchi, and K.Inomata,: "Asymmetric Bis (alkoxycarbonylation) Reaction of Homoallylic Alcohols Catalyzed by Palladium in the Presence of Cu(I) Triflate Using the Chiral Bioxazoline Ligand" Bull.Chem.Soc.Jpn.69. 735-742 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Ukaji, Y.Kenmoku, and K.Inomata,: "Asymmetric Addition Reaction of Organozinc Reagents to Nitrones Using a Catalytic Amount of External Chiral Auxiliary" Tetrahedron : Asymmetry. 7. 53-56 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Inomata: "Development of the Asymmetric Cycloaddition Reactions and Asymmetric Nucleophilic Addition Reaction Utilizing Tartaric Acid Esters." J.Synth.Org.Chem.Jpn.56. 11-21 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Ukaji: "Enantio- and Diastereoselective Synthesis of Isoxazolildines by Asymmetric 1,3-Dipolar Cycloaddition of Nitrones." Chem.Lett.547-548 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] A.Shibayama: ""Syn-Effect" in the Desulfonylation Reaction of alpha, alpha-Dialkylated (E) -Allyic Sulfones." Bull.Chem.Soc.Jpn.70. 381-396 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Ukaji: "Design of the Chiral Reaction Field Utililzing Tartaric Acid Esters." Kagaku to Kogyo. 50. 167-170 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Ukaji: "Catalytic Asymmetric Addition Reaction of Dialkylzinc to Nitrone Utilizing Tartaric Acid Ester as a Chiral Auxiliary" Chem.Lett.59-60 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] M.Shimizu: "Catalytic Asymmetric 1,3-Dipolar Cycloaddition of Nitrile Oxide to an Achiral Allyl Alcohol Utilizing Diisopropyl Tartrate as a Chiral Auxiliary." Chem.Lett.455-456 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Ukaji: "Asymmetric Bis (alkoxycarbonylation) Reaction of Homoallylic Alcohols Catalyzed by Palladium in the Presence of Cu (I) Triflate Using the Chiral Bioxazoline Ligand" Bull.Chem.Soc.Jpn.69. 735-742 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Ukaji: "Asymmetric Addition Reaction of Organozinc Reagents to Nitrones Using a Catalytic Amount of External Chiral Auxiliary." Tetrahedron : Asymmetry. 7. 53-56 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Inomata and Y.Ukaji: "Development of the Asymmetric Cycloaddition Reactions and Asymmetric Nucleophilic Addition Reaction Utilizing Tartaric Acid Esters" J.Synth.Org.Chem.Jpn,. 56. 11-21 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Ukaji: "Design of the Chiral Reactions Field Utilizing Tartaric Acid Esters" Kagaku to Kogyo. 50. 167-170 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] A.Shibayama, T Nakamura, T.Shintani, Y.Ukaji, H.Kinoshita, and K.Inomata et al: "“Syn-Effect"in the Desulfonylation Reactions of α,α-Dialkylated(E)-Allyic Sulfones" Bull.Chem.Soc.Jpn.70. 381-396 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Ukaji, K.Taniguchi, K.Sada, and K.Inomata: "Enantio-and Diastereoselective Synthesis of Isoxazolidines by Asymmetric 1,3-Dipolar Cycloaddition of Nitrones" Chem.Lett.1997. 547-548 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Y.Ukaji, Y.Shimizu, Y.Kenmoku, A.Ahmed, and K.Inomata: "Catalytic Asymmetric Addition Reaction of Dialkylzinc to Nitrone Utilizing Tartaric Acid Esters as a Chiral Auxiliary" Chem.Lett.1997. 59-60 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] A.Shibayama,Y.Ukaji,H.Kinoshita,K.Inomata,et al: ""Syn-Effect" in the Desulfonylation Reaction of α,α-Dialkylated (E)-Allyic Sulfones" Bull.Chem.Soc.Jpn.70. 381-396 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Y.Ukaji,Y.Shimizu,Y.Kenmoku,A.Ahmed,and K.Inomata: "Catalytic Asymmetric Addition Reaction of Dialkylzinc to Nitrone Utilizing Tartaric Acid Ester as a Chiral Auxiliary" Chem.Lett.59-60 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Shimizu,Y.Ukaji,and K.Inomata: "Catalytic Asymmetric 1,3-Dipolar Cycloaddition of Nitrile Oxide to an Achiral Allyl Alcohol Utilizing Diisopropyl Tartrate as a Chiral Auxiliary" Chem.Lett.455-456 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Y.Ukaji,M.Miyamoto,M.Mikuni,S.Takeuchi,and K.Inomata: "Asymmetric Bis (alkoxycarbonylation) Reaction of Homoallylic Alcohols Catalyzed by Palladium in the Presence of Cu(I) Triflate Using the Chiral Bioxazoline Ligand" Bull.Chem.Soc.Jpn.69. 735-742 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Y.Ukaji,Y.Kenmoku,and K.Inomata: "Asymmetric Addition Reaction of Organozinc Reagents to Nitrones Using a Catalytic Amount of External Chiral Auxiliary" Tetrahedron:Asymmetry. 7. 53-56 (1996)

    • Related Report
      1996 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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