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Creation of Enantioselective Cross- Coupling Reactions in the Solid State

Research Project

Project/Area Number 13640595
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 物質変換
Research InstitutionOKAYAMA UNIVERSITY OF SCIENCE

Principal Investigator

TODA Fumio  OKAYAMA UNIVERSITY OF SCIENCE Department of Chemiatry, Professor, 理学部, 教授 (50036232)

Co-Investigator(Kenkyū-buntansha) TOYOTA Shinji  OKAYAMA UNIVERSITY OF SCIENCE Department of Chemiatry, Professor, 理学部, 教授 (80207646)
Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2002: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2001: ¥2,000,000 (Direct Cost: ¥2,000,000)
Keywordscross-coupling reaction / enantioselective reaction / host-guest complex / solvent-free reaction / solid state reaction / tautomerism / monitoring by spectrum / analysis of reaction mechanism / 不斉選択的反応 / 個体反応 / 交差カップリング固相反応 / ホスト化合物 / 多分子包接化合物 / アセチレンアルコールホスト / ビス-β-ナフトールホスト / キンヒドロンタイプの包接結晶 / クレゾール誘導体ホスト / 低分子有機化合物
Research Abstract

Firstly, various organic neactions were carried out in the solid state in order to develop organic solid state reactions. When substrate and / or reagent is liquid, reaction between them was carred out under solvent-free conditions. Sililation reaction of alcohols proceeded efficriently just by mixing of alcohol and trialkylsilyl chloride. Claisen, Thorpe and Cannizzaro reactions were also found to proceed efficiently under solvent-free conditions. Cross-Claisen and Thorpe reactions were also successful. By monitoring of a solvent-free Thorpe reaction by continuous measurements of IR spectra, reaction intermediate was detected and reaction mechanism was clarified. Real solid state reaction is also effective. For example, FeCIa-catalyzed coupling reaction of 2-naphthol proceeded in the solid state very efficiently and its dimer 2, 2' -dihydroxy- 1, -binapthyl was obtained in good yield. However, coss-coupling reaction of 2-naphthol and 1, 2 -naphthalenediol in the solid state gave a complex mixture. Inclusion complexation of two different guest molecules by a host to give an interesting complex consisted of three different components. Unfortunately, however, cross-coupling reaction of the two tautomers was unsuccessful. When chiral host is used for such the cross-coupling reaction in the solid state, enantioselective solvent-free cross-coupling reaction can be accomplished. We are going to design such the dreamy reaction

Report

(3 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • Research Products

    (29 results)

All Other

All Publications (29 results)

  • [Publications] K.Yoshizawa, S.Toyota, F.Toda: "Solvent-free Claisen and Cannizzaro reactions"Tetrahedron Lett.. 42. 7983-7985 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] B.Hatano, S.Toyota, F.Toda: "Efficient solvent-free O-sililation of alcohols with R_3SiCl"Green Chem.. 3. 140-142 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Kato, K.Tanaka, F.Toda: "Stereoselective Inclusion and Structure of Equatorial-t-1, 2-dichlorocyclohexane"Supramol. Chem.. 175-180 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Yoshizawa, S.Toyota, F.Toda: "Efficient solvent-free Thorpe reactions"Green Chem.. 4. 68-70 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N.Shan, F.Toda, W.Jones: "Mechanochemistry and co-crystal fonnation : effect of solvent"Chem. Commun.. 2374-2375 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] F.Toda: "Crystal engineering for molecular dynamics"Cryst Eng Comm. 4. 215-222 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] F.Toda (ed): "Organic Solid State Reactions"Kluwer Academic Publishers. 275 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Yoshizawa, S. Toyota, F. Toda: "Solvent-free Claisen and Cannizzaro reactions"Tetrahedron Lett. 42. 7983-7985 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] B. Hatano, S. Toyota, F. Toda: "Efficient solvent-free O-sililation of alcohols with RsSiCl"Green Chem. 3. 140-142 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Kato, K. Tanaka, F. Toda: "Stereoselective Inclusion and Structure of Equatorial -t- 1, 2 -dicholorocyclohexane"Supramol. Chem. 175-180 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K. Yoshizawa, S. Toyota, E. Toda: "Efficient solvent-free Thorpe reactions"Green. Chem. 4. 68-70 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N. Shan, F. Toda, W. Jones: "Mechanochemistry and co-crystal formation: effect of solvent on reaction kinetics"Chem. Commun. 2374-2375 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] F. Toda: "Crystal engineering for molecular Dynamics"CrystEngComm. 4. 215-222 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] F. Toda, K. Tanaka, H. Miyamoto: "Enantioselective Photoreactions"Mercel Dekker. (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] F. Toda: "Organic Solid State Reactions"Kluwer Academic Publishers. (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Yoshizawa, S.Toyota, F.Toda: "Solvent-free Claisen and Cannizzaro reactions"Thtrahedron Left.. 42. 7983-7985 (2001)

    • Related Report
      2002 Annual Research Report
  • [Publications] B.Hatano, S.Toyota, F.Toda: "Efficient solvent-free O-sililation of alcohols with R_3SiCl"Green Chem.. 3. 140-142 (2001)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Kato, K.Tanaka, F.Toda: "Stereoselective Inclusion and Structure of Equtorial-t-1,2-dichloroclohexane"Supramol. Chem.. 175-180 (2001)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Yoshizawa, S.Toyota, F.Toda: "Efficient solvent-free Thorpe reactions"Green Chem.. 4. 68-70 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] N.Shan, F.Toda, W.Jones: "Mechanochemistry and co-crystal formation:effect of solvent on reaction kinetics"Chem. Commun.. 2374-2375 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] F.Toda: "Crystal engineering for molecular dynamics"CystEngComm. 4. 215-222 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] F.Toda, K.Tanaka, H.Miyamoto: "Enantioselective Photoreactions in the Solid State"Marcel Dekker. 757 (2001)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Toyota, H.Sawa, M.Asakura, S.Hirano, F.Toda: "Crystal structures of 2 : 1 inclusion complexes of xylidine isomers with 1, 1, 6, 6-tetraphenylhexa-2, 4-diyne-1, 6-diol : the importance of weak intermolecular interactions on crystal stability"CrystEngComm. 7. (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] K.Tanaka, M.Kato, F.Toda: "Optical Resolution of 2-Azabicyclo[2. 2. 1]hept-5-en-3-one by Inclusion Complexation with Brucine"Heterocycles. 54. 405-410 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Kato, K.Tanaka, F.Toda: "Stereoselective Inclusion and Structure of Equatorial-trans-1, 2-dichlorocyclohexane"Supramol. Chem.. 13. 175-180 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] K.Tanaka, M.Kato, F.Toda: "Induced Circular Dichroism in Solid-State Inclusion Compounds"Chirality. 13. 347-350 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] B.Hatano, S.Hirano, T.Yanagihara, S.Toyota, F.Toda: "Attempted Selective Photodimerization of 2-Quinolone in Inclusion Crystals with Host Compounds : X-ray Structural Study of Inclusion Crystals"Synthesis. 1181-1184 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.R.Caira, L.R.Nassimbeni, F.Toda, D.Vujovic: "Inclusion by a diol host compound : structure and dynamics of volatile guest exchange"J. Chem. Soc., Perkin Trans. 2. 2219-2124 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] F.Toda, K.Tanaka, H.Miyamoto: "Understanding and Manipulating Excited-State Processes"V.Ramamurthy, Kirk S.Schanze Marcel Dekker. 41(385-425) (2001)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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