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Development of Novel Synthetic Organic Reactions by Means of Rare Earth Metal Complexes

Research Project

Project/Area Number 61550642
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionKyushu University

Principal Investigator

FUJIWARA Yuzo  Kyushu University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (10029481)

Co-Investigator(Kenkyū-buntansha) ISOMURA Kazuaki  Kyushu University, Faculty of Engineering, Assistant Professor, 工学部, 講師 (80037887)
Project Period (FY) 1986 – 1987
Project Status Completed (Fiscal Year 1987)
Budget Amount *help
¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1987: ¥100,000 (Direct Cost: ¥100,000)
Fiscal Year 1986: ¥1,500,000 (Direct Cost: ¥1,500,000)
KeywordsTrichlorolanthanoids as Friedel-Crafts Catalysts / Ytterbium Mediated Reduction of Multiple Bonds / Yb金属による芳香属ケトンの極性変換 / 非対称ピナコール合成 / 再使用可能なフリーデル・クラフツ触媒 / ランタノイド塩化物 / フリーデル・クラフツ触媒 / 希土類塩化物によるフリーデル・クラフツ反応 / 回収・再使用可能触媒 / 三塩化ルテチゥム / 三塩化ジスプロシウム / 三塩化イッテルビウム / 三塩化ガドリニウム
Research Abstract

By studies on this project, the following novel synthetic reactions are explored by utilizing rare earth metals and their complexes:
1. Trichlorolanthanoid(LnCl_3) Catalyzed Friedel-Crafts Alkylation and Acylation.
LnCl_3 including all the rare earths except Pm, have been found to be good catalysts for Friedel-Crafts alkylation and acylation of aromatic compounds such as benzene and furan. Characteristic feature of those catalysts is that they can be recovered after the reaction without decomposition and can be reused repeatedly.
2. Convenient Reduction of C-C Multiple Bonds Conjugated with Aromatic Rings by PhYbI Complex or Yb Metal.
PhYbI/MeOH or Yb/MeOH causes reduction of aromatic-substituted olefins and acetylenes to give the corresponding alkanes. The use of MeOD gives deuteriated alkanes in quantitative yields.
3. Ytterbium Mediated Synthesis of Symmetrical and Unsymmetrical Pinacols from Carbonyl Compounds.
Reaction of Yb metal with aromatic ketones such as benzophenone gives in situ metallacycle intermediates(KA) which undergo coupling with a variety of ketones to give symmetrical and unsymmetrical pinacols in high yields. This is the first example of the reaction in which polarity of ketones is changed from positive to negative by Yb. Furthermore it has been found that the metallacycle intermediates can react with not only ketones but also a variety of electrophiles such as nitriles, epoxides, CO_2 etc.
Through this project, rare earth mediated novel and very useful reactions have been developed.

Report

(2 results)
  • 1987 Final Research Report Summary
  • 1986 Annual Research Report
  • Research Products

    (18 results)

All Other

All Publications (18 results)

  • [Publications] 三根法興: Chemistry Letters. 357-360 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] 侯召民: Chemistry Letters. 305-308 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] 侯召民: J.Org.Chem.1987. (3524-3528)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] 侯召民: Chemistry Letters. 2061-2064 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] 侯召民: J.Org.Chem.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] 侯召民: J.Chem.Soc.,Chem.Commun.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] 大塚,中村,山崎,藤原祐三共編: "化学増刊109「錯体触媒化学の進歩」分担"ランタノイド触媒"" (株)化学同人(植下定一), 270 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Norioki Mine: "Trichlorolanthanoid(LnCl_3)-Catalyzed Friedel-Crafts Reactions" Chemistry Letters. 357-360 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Zhaomin Hou: "Convenient Reduction of C-C Multiple Bonds Conjugated with Aromatic Rings by PhYbI Complex or Yb Metal" Chemistry Letters. 305-308 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Zhaomin Hou: "Chemistry of Organolanthanoids. Lanthanoid Mediated C-C Bond Formation,Cleavage, and C-C Double Bond Reduction" J. Organic Chemistry. 52. 3524-3528 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Zhaomin Hou: "Ytterbium Mediated Synthesis of Symmetrical and Unsymmetrical Pinacols from Carbonyl Compounds" Chemistry Letters. 2061-2064 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Zhaomin Hou: "Lanthanoid in Organic Synthesis. Samarium Metal Promoted Selective Formation of Azoxy Compounds" J. Organic Chemistry submitted.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] Yuzo Fujiwara (edited by Otsuka, Nakamura, Yamazaki): "Lanthanoid Catalysts" in Progress in Transition Metal Complex Catalysts(Kagaku-Zokan 109). Kagaku Dojin, Kyoto, Japan, 241-255 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1987 Final Research Report Summary
  • [Publications] 三根法興: Chemistry Letters. 1986. 357-360 (1986)

    • Related Report
      1986 Annual Research Report
  • [Publications] 侯召民: Chemistry Letters. 1987. 305-308 (1987)

    • Related Report
      1986 Annual Research Report
  • [Publications] 侯召民: J.Chem.Soc.,Chemical Communications.

    • Related Report
      1986 Annual Research Report
  • [Publications] 侯召民: J.Am.Chem.Soc.

    • Related Report
      1986 Annual Research Report
  • [Publications] 大塚,中村,山崎 編 藤原祐三: "化学増刊109「錯体触媒化学の進歩」"ランタノイド触媒"" (株)化学同人 植下定一, 270 (1986)

    • Related Report
      1986 Annual Research Report

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Published: 1987-03-31   Modified: 2016-04-21  

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