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Formation of Radical from Photoinduced Electron Transfer Reaction and its Application for Organic Synthesis

Research Project

Project/Area Number 11640535
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

TAKUWA Akio  Shimane university, Fac. Sci & Eng., Professor, 総合理工学部, 教授 (70032456)

Co-Investigator(Kenkyū-buntansha) IWAMOTO Hidetoshi  Shimane university, Fac. Sci & Eng., Assistant Professor, 総合理工学部, 助教授 (00032623)
NISHIGAICHI Yutaka  Shimane university, Fac. Sci & Eng., Assistant professor, 総合理工学部, 助教授 (00212118)
Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 2000: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1999: ¥1,800,000 (Direct Cost: ¥1,800,000)
Keywords1, 2-diketone / allylsilane / allylstannane / 1, 2-naphthoquinone / allylation / allylic radical / photoinduced electron transfer / α-ジケトン / 14族金属複合試薬 / フリル化反応 / 光付加反応 / アリシラン / 光電子移動 / アリル化反応
Research Abstract

In this research project, we found the following regio-and stereo-selective synthesis using radical species produced by photoinduced single electron transfer (SET) reactions.
1. Irradiation of a CH_3CN solution of a-diketones and allylsilane/allylstannane-bifunctional reagent which possesses both allylic silane and allylic stannane functionality in the same molecule sharing the same carbon-carbon double bond afforded α-ketohomoallyl alcohol having allylsilane moiety in good yields. These results indicate that the (alkyl) C-Sn bond rather than (alkyl) C-Si bond of the cation radial formed by photoinduced SET reaction of the bifunctional reagent cleavages selectively to give allylic radical having allylsilane moiety, and the resulting allylic radical couples with semidione radical to form the α-ketohomoallyl alcohol. When the treatment of the irradiated mixture with Mg(CO_4)_2 cis-methylenecyclopentane-1, 2-diols were obtained, whereas the treatment with tetrabutylammonium fluoride (TBAF) yielded trans-1, 2-diols.
2. 1, 2-Naphthoquinone reacted with γ-substituted allyltin reagents in both thermal and photochemical conditions to yield 4-allyl-1, 2-naphthoquinone. The opposite regioselectivity of introduced allylic moiety was observed in both reaction conditions.
3. The photochemical reaction of 1, 2-naphthoquinones with allylsilanes afforded [3+2] cycloadducts via diradical intermediate, which was converted to 3-allyl-1, 2-naphthoquinones in moderate to good overall yields by treatment with boron trifluoride, ammonium cerium nitrate or TBAF.

Report

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

    (9 results)

All Other

All Publications (9 results)

  • [Publications] Akio Takuwa: "Allylsilylation and Stannylation of 1,2-Diketones using Bifunctional Allylsilane-Allylstannane Reagents via Photoinduced Electron Transfer Reaction"J.Chem.Soc.,Chem.Commun.. 1999. 1963-1964 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Yutaka Nishigaichi: "Contrasting Regiochemistry in Thermal and Photochemical Allylstannation of 1,2-Naphthoquinones"Chem.Lett.. 1999. 803-804 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Akio Takuwa: "Regioselective Allylation of 1,2-Naphthoquinones using Phtoaddition Reactions with Allylsilanes : Synthesis of 3-Allyl-1,2-naphthoquinones"Synthesis. 2001. 63-68 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] A.Takuwa: "Allylsilylation and Stannylation of 1, 2-Diketones using Bifunctional Allylsilane-Allyl stannnane Reagents via Photoinduced Electron Transfer Reaction"Chem.Commun.. 1963-1964 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Y.Nishigaichi: "Contrasting Regiochemisty in Thermal and Photochemical Allylstannation of 1, 2-Naphthoquinones"Chem.Lett.. 803-804 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] A.Takuwa: "Regioselective Allylation of 1, 2-Naphthoquinones using Phtoaddition Reaction with Allylsilanes : Synthesis of 3-Allyl-1, 2-naphthoquinones"Synthesis. 63-68 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Akio Takuwa: "Regioselective Allylation of 1,2-Naphtoquinones using Photoaddition Reaction with Allylsilanes : Synthesis of 3-Allyl-1,2-naphthoquinones"J.Synth.Org.Chem.. 2001. 63-68 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] Akio Takuwa: "Allylsilation and Stannylation of 1,2-Diketones using Bifunctional Allylsilane-Allylstannane Reagents via Photoinduced Electron Transfer Reaction"Chemical Communications. 1999. 1963-1964 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Yutaka Nishigaichi: "Contrasting Regiochemistry in Thermal and Photochemical Allylstannations of 1,2-naphthoquinone"Chemistry Letters. 1999. 803-804 (1999)

    • Related Report
      1999 Annual Research Report

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

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