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Design of Metal Artificial Enzymes and the Application to Fine Organic Synthesis

Research Project

Project/Area Number 11440184
Research Category

Grant-in-Aid for Scientific Research (B).

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKYOTO UNIVERSITY (2000)
Hokkaido University (1999)

Principal Investigator

MARUOKA Keiji  Kyoto Univ., Grad. Sch. of Sci., Professor, 大学院・理学研究科, 教授 (20135304)

Co-Investigator(Kenkyū-buntansha) OOI Takashi  Kyoto Univ., Grad. Sch. of Sci., Assoc. Professor, 大学院・理学研究科, 助教授 (80271708)
近藤 裕一郎  北海道大学, 大学院・理学研究科, 助手 (90301928)
Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥16,100,000 (Direct Cost: ¥16,100,000)
Fiscal Year 2000: ¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 1999: ¥10,100,000 (Direct Cost: ¥10,100,000)
Keywordsorganic synthesis / alkyl halides / carbon-centered radicals / anchimeric effect / carbanion species / アニオン種 / ヘテロ原子 / セレン / テルル / 金属ハロゲン交換 / 炭素炭素結合形成
Research Abstract

Alkyl halides, especially iodides and bromides, are frequently utilized as precursors to generate various carbon-centered radicals in organic synthesis. The usefulness of these halo derivatives in radical reactions has been demonstrated in numerous synthetic examples and often reviewed in the chemical literature. There is, however, inevitable drawback to the use of such reactive alkyl halides for radical reactions, and this is mainly due to the troublesome intervention of internal and/or external nucleophiles (e.g., alkoxides, amines, cyanide, enolates, etc.). To overcome this intrinsic problem, we initiated the search for a reactive alkyl iodide equivalent which is stable for ordinary nucleophilic attack. Herein we wish to report that ο-(ο-iodophenyl)phenylthio derivatives are highly effective with various functional group compatibility for rapid generation of carbon radicals under mild conditions. This approach expands the scope of radical chemistry, since a variety of nucleophilic t … More hiolations (thioacetalization, conjugate addition, epoxide opening, etc.) using arythiol can be readily combined with the present radical generation process. In addition to ο-(ο-iodophenyl)phenylthio derivatives, ο-[(E)-2-Trimethylsilyl-2-iodovinyl]phenylthio derivatives have been also introduced as effective precursors for the generation of carbon centered radicals even in the presence of certain nucleophiles ; this provides useful information about the structural requirement for inducing an efficient anchimeric effect under mild conditions.
The above mentioned chemistry led us to investigate the possibility of generating desired carbanion species by the utilization of such anchimeric effect. Taking both the versatility and the availability with the limitation of structural types into account, we focused on the combined use of ο-(ο-iodophenyl)phenylselenenyl or tellurenyl derivatives and commercially available alkyllithiums, expecting that various alkyllithium reagents could be efficiently prepared through the initial Li-halogen exchange and subsequent translocation of the resulting anion. The synthetic utility as well as the limitation were evaluated in the in situ trapping reaction with carbonyl compounds. Less

Report

(3 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • Research Products

    (5 results)

All Other

All Publications (5 results)

  • [Publications] Takashi Ooi: "Rapid and Mild Generation of Carbon Radicals from o-(o-Iodophenyl) Anchimeric Approach phenylthio Derivatives by an"Advanced Synthesis & Catalysis. (発表予定).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takashi Ooi: "Utilization of o-[(E)-2-Trimethylsilyl-2-iodovinyl]phenylthio Derivatives as Carbon Radical Precursors by Anchimeric Approach"SYNLETT. (発表予定).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ooi: "Rapid and Mild Generation of Carbon Radicals from ο-(ο-Iodophenyl) phenylthio Derivatives by an Anchimeric Approach"Advanced Synthesis & Catalysis. (in press.).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ooi: "Utilization of ο-[(E)-2-Trimethylsilyl-2-iodovinyl] phenylthio Derivatives as Carbon Radical Precursors by Anchimeric Approach"SYNLETT. (in press.).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Takashi Ooi: "Utilization of o-[(E)-2-Trimethylsilyl-2-iodovinyl] phenylthio Derivatives as Carbon Radical Precursors by Anchimeric Approach"SYNLETT. (発表予定).

    • Related Report
      2000 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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