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Development and Application of Coupling Reactions via Carbon-Carbon Bond Ceavage

Research Project

Project/Area Number 09440212
Research Category

Grant-in-Aid for Scientific Research (B)

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

Principal Investigator

TAKAHASHI Tamotsu  Hokkaido Univ., Catalysis Research Center., Pro., 触媒化学研究センター, 教授 (30163273)

Co-Investigator(Kenkyū-buntansha) HARA Ryuichiro  Hokkaido Univ., Cataiysis Research Center., Inst., 触媒化学研究センター, 助手 (30281851)
KOTORA Martin  Hokkaido Univ., Catalysis Research Center., Asso. Pro., 触媒化学研究センター, 助教授 (60281846)
席 振峰  北海道大学, 触媒化学研究センター, 助手 (90292060)
Project Period (FY) 1997 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥11,500,000 (Direct Cost: ¥11,500,000)
Fiscal Year 1999: ¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1998: ¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1997: ¥6,900,000 (Direct Cost: ¥6,900,000)
Keywordszirconium / crabon-carbon bond cleavage / zirconacycles / dihalopyridine / quinoline / isoquinoline / zirconacyclopentadienes / ジルコナシクロペンタジュン / ジルコニウム錯体 / シルコノセン・エチレン錯体 / ジルコナシクロペンテン / 不飽和ケトン / ホモアリルアルコール / 炭素-炭素結合の活性化 / 炭素-炭素結合生成反応 / 単結晶X線構造解析 / 炭素炭素結合切断 / ジルコナミクロペンテン / ジエン / アセチレン / ビニルブロミド / カップリング / ビニル基
Research Abstract

When two of unsaturated compounds couple on zirconocene (II), five-membered zirconacycles were formed in high yields. Carbon-carbon bond cleavage of the zirconacycles followed by the second coupling with another unsaturated compounds afforded various types of zirconacycles. In particular, when the direct coupling of two unsaturated compounds is difficult, our method developed is very useful. In this project we developed further useful reactions. Pyridines with two halogens at C2 and C3 carbons reacted with zirconacyclopentadienes in the presence of CuCl, new two carbon-carbon bonds were formed at C2 and C3 carbons. Quinoline derivatives were formed in high yields. When 3,4-dihalopyridines were used, isoquinoline derivatives were obtained in a similar manner. For these reactions, various substituents could be used. Not only monocyclic zirconacyclopentadienes, but also bicyclic zirconacyclopentadienes reacted without any problems.

Report

(4 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (19 results)

All Other

All Publications (19 results)

  • [Publications] 高橋保: "Reaction of Zirconacyclopentadienes with CO in the Presence of n-BuLi. Formation of Cyclopentenone Derivatives from Two Alkynes and CO"J.Am.Chem.Soc.. 121. 1094-1095 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 高橋保: "Carbon-carbon Bond Formation of Zirconacyclopentadienes with Alkynes in the Presence of Ni(II)-complexes"J.Am.Chem.Soc.. 121. 11093-11100 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 高橋保: "Inter or Intramolecular Carbometalation of Non-activated Alkynes by Zirconacyclopentanes in the Presence of Copper Salt"Augew.Chem. Int.Ed. 38. 949-952 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 高橋保: "Reaction of Oxazirconacyclopentenes with Propynoates. A New Pathway for the Formation of 2,5-Dihydrofuran Derivatives"Tetrahedron Lett.. 40. 2375-2378 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 高橋保: "Formation of Cyclooctatetraenes from Zirconacyclopentadienes"Chem.Commun.. 1595-1596 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 高橋保: "A Convenient One-Pot Procedure to Arylcyclobutenes from Arylacetylenes"J.Org.Chem.. 64. 8706-8708 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] TAKAHASHI Tamotsu: "Reaction of Zirconacyclopentadienes with CO in the Presence of n-BuLi. Formation of Cyclopentenone Derivatives from Two Alkynes and CO"J. Am. Chem. Soc.. 121. 1094-1095 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] TAKAHASHI Tamotsu: "Carbon-carbon Bond Formation of Zirconacyclopentadienes with Alkynes in the Presence of Ni(II)-complexes"J. Am. Chem. Soc.. 121. 11093-11100 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] TAKAHASHI Tamotsu: "Inter or Intramolecular Carbometalation of Non-activated Alkynes by Zirconacyclopentanes in the Presence of Copper Salt"Angew. Chem. Int.. 38. 949-952 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] TAKAHASHI Tamotsu: "Reaction of Oxazirconacyclopentenes with Propynoates. A New Pathway for the Formation of 2,5-Dihydrofuran Derivatives"Tetrahedron Lett.. 40. 2375-2378 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] TAKAHASHI Tamotsu: "Formation of Cyclooctatetraenes from Zirconacyclopentadienes"Chem. Commun.. 1595-1596 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] TAKAHASHI Tamotsu: "A Convenient One-Pot Procedure to Arylcyclobutenes from Arylacetylenes"J. Org. Chem.. 64. 8706-8708 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 高橋 保: "Reaction of Zirconacyclopentadienes with CO in the Presence of n-BuLi. Formation of Cyclopentenone Derivatives from Two Alkynes and CO"J. Am. Chem. Soc.. 121. 1094-1095 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 高橋 保: "Carbon-carbon Bond Formation of Zirconacyclopentadienes with Alkynes in the Presence of Ni(II)-complexes"J. Am. Chem. Soc.. 121. 11093-11100 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 高橋 保: "Inter or Intramolecular Carbometalation of Non-activated Alkynes by Zirconacyclopentanes in the Presence of Copper Salt"Angew. Chem. Int. Ed. 38. 949-952 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 高橋 保: "Reaction of Oxazirconacyclopentenes with Propynoates. A New Pathway for the Formation of 2,5-Dihydrofuran Derivatives"Tetrahedron Lett.. 40. 2375-2378 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 高橋 保: ""Formation of Cyclooctatetraenes from Zirconacyclopentadienes""Chem. Commun.. 1595-1596 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 高橋 保: "A Convenient One-Pot Procedure to Arylcyclobutenes from Arylacetylenes"J. Org. Chem.. 64. 8706-8708 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 高橋 保: "Intermolecular Coupling Reaction of Alkynes with Viuyl Bromide with Selective Skeletal Rearrangement" J.Am.Chem.Soc.119. 4561-4562 (1997)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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