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Synthesis of novel transition metal dinuclear complex catalyst and application to organic synthesis

Research Project

Project/Area Number 14550816
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionTohoku University

Principal Investigator

INOUE Yoshio  Tohoku University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (50005518)

Co-Investigator(Kenkyū-buntansha) TSUKADA Naofumi  Tohoku University, Graduate School of Engineering, Assistant Professor, 大学院・工学研究科, 助手 (70292240)
Project Period (FY) 2002 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2004: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2003: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2002: ¥1,500,000 (Direct Cost: ¥1,500,000)
KeywordsDinuclear Complex / Palladium / Platinum / Rhodium / C-H Activation / Hydroarylation / Alkyne / Aromatic Ring / 芳香族化合物 / ダブルカルボニル化
Research Abstract

We have exploited a novel tetradentate ligand (Hdpfam) containing nitrogen and phosphorus donor atoms. Several dinuclear complexes (M_2Ar_2(η-X)(η-dpfam), M=Pd, Pt, Rh) can be synthesized using this ligand. Development of catalytic reactions utilizing the dinuclear complexes mediated only by dinuclear system has been studied and the following results are obtained.
1.Hydrosilylation of alkynes catalyzed by dinuclear platinum complex
Dinuclear platinum hydride complex Pt_2Tbl_2(η-H)(η-dpfam)) obtained by treatment of the chloride bridged platinum dinuclear complex with sodium borohydride was found to be a good catalyst for the hydrosilylation of alkynes.
2.Activation of C-H bond of aromatic compounds by dinuclear palladium complexes
Dinuclear palladium complexes were found active far hydroarylation of alkynes activating the C-H bond of an aromatic ring which was usually regarded inert. Elucidation of the reaction mechanism uncovered that the reaction proceeds with direct C-H bond activation by palladium center.
3.Activation of C-H bond of alkenes
Dinuclear palladium complexes were found active for hydroalkenylation of alkynes activating the C-H bond of an alkene double bond which was usually regarded inert.
4.Suzuki-Miyaura reaction catalyzed by dinuclear palladium complex
Dinuclear palladium complexes catalyzed the Suzuki-miyaura reaction in benzene solvent to give a cine product together with the normal one.
5.Double carbonylation catalyzed by dinuclear palladium complex
Dinuclear palladium complex was found to be an active catalyst for the double carbonylation of iodobenzene with diethylamine.

Report

(4 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (15 results)

All 2003 2002 Other

All Journal Article (9 results) Publications (6 results)

  • [Journal Article] Palladium-catalyzed 1,6- and 1,5-diyne-carbon monoxide reaction for preparation of alkylidenecyclopentenones and -butenolides2003

    • Author(s)
      S.Sugawara
    • Journal Title

      Journal of Molecular Catalysis A.Chemical 195

      Pages: 55-61

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Palladium-Catalyzed Benzannulation from Alkynes and Allylic Compounds2003

    • Author(s)
      Naofumi Tsukada
    • Journal Title

      The Journal of Organic Chemistry 68

      Pages: 5961-5966

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Rhodium- and Iridium-Catalyzed Allylation of Electron-Rich Arenes with Allyl Tosylate2003

    • Author(s)
      Naofumi Tsukada
    • Journal Title

      Synlett 2003

      Pages: 1431-1434

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Palladium-catalyzed allylic alkenylation of allylic alcohols with n-butyl acrylate2003

    • Author(s)
      Naofumi Tsukada
    • Journal Title

      Chemical Communications 2003

      Pages: 2404-2405

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Stereoselective cis-Addition of Aromatic C-H Bonds to Alkynes Catalyzed by Dinuclear Palladium Complexes2003

    • Author(s)
      Naofumi Tsukada
    • Journal Title

      Journal of the American Chemical Society 125

      Pages: 12102-12103

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Double carbonylation of aryl iodides with diethylamine catalyzed by dinuclear palladium complexes2003

    • Author(s)
      Naofumi Tsukada
    • Journal Title

      Journal of Organometallic Chemistry 687

      Pages: 436-443

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Palladium-catalyzed 1,6-and 1,5-diyne-carbon monoxide reaction for preparation of alkylidenecyclopentenones and -butenolides2003

    • Author(s)
      S.Sugawara
    • Journal Title

      Journal of Molecular Catalysis A.Chemical 195

      Pages: 55-61

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Rhodium-and Iridiumu-Catalyzed Allylation of Electron-Rich Arenes with Allyl Tosylate2003

    • Author(s)
      Naofumi Tsukada
    • Journal Title

      Synlett 2003

      Pages: 1431-1434

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synthesis and Structures of Palladium and Platinum A-Frame Complexes Bridged by a Novel Binuleating Ligand2002

    • Author(s)
      Naofumi Tsukada
    • Journal Title

      Organometallics 21

      Pages: 2521-2528

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Publications] Naofumi Tsukada: "Stereoselective cis-Addition of Aromatic C-H Bonds to Alkynes Catalyzed by Dinuclear Palladium Complexes"Journal of the American Chemical Society. 125. 12102-12103 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Naofumi Tsukada: "Double Carbonylation of Aryl Iodides with Diethylamine Catalyzed by Dinuclear Palladium Complexes"Journal of Organometallic Chemistry. 687. 436-443 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Shuichi Oi: "Rhodium-catalyzed conjugate addition of aryl-and alkenylstannanes to α,β-unsaturated carbonyl compounds"Tetrahedron. 58,1. 91-97 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Shuichi Oi: "Conjugate Addition of Organosiloxanes to α,β-Unsaturated Carbonyl Compounds Catalyzed by a Cationic Rhodium Complex"Organic Letters. 4,4. 667-669 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Shuichi Oi: "Ruthenium Complex Catalyzed Direct Ortho Arylation and Alkenylation of Aromatic Imines with Organic Halides"Organic Letters. 4,10. 1783-1785 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Shuichi Oi: "Asymmetric 1,4-Addition of Organosiloxanes to α,β-Unsaturated Carbonyl Compounds Catalyzed by a Chiral Rhodium Complex"Organic Letters. 5,1. 97-99 (2003)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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