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Development of Novel Photoelectron Transfer Reaction Systems with Stable Organometallic Compounds Promoted by Acids and Bass

Research Project

Project/Area Number 12640519
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

NISHIGAICHI Yutaka  Shimane University, Interdisciplinary Faculty of Science and Engineering, Associate Professor, 総合理工学部, 助教授 (00212118)

Project Period (FY) 2000 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2002: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2001: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 2000: ¥1,600,000 (Direct Cost: ¥1,600,000)
KeywordsPhotoreaction / Electron Transfer / Organotin Compounds / Organosilicon Compounds / Organoboron Compounds / Hypervalence / Lewis Acid / Lewis Base / 有機スズ化合物 / 有機ホウ素化合物 / 高配位化合物 / アリルスズ化合物 / アリルケイ素化合物 / カルボニル化合物 / 隣接基関与 / アリルスズ / 水素結合 / 配位 / 金属イオン
Research Abstract

The effect of basic (nucleophilic) moieties on the activation of organometallic reagents in the photoinduced electron transfer (PET) reaction toward aromatic ketones was investigated. For allyl- and benzyltin reagents, the presence of hydroxyl group at the near position increased the efficiency of the reaction. For allylsilicon reagents, introduction of the 5th ligand into them accelerated the PET reaction efficiently and gave the allylated product in high yields. These reactions also contained the characteristic feature of PET, α-regioselectivity and stereoretention of the double bond in allyl moiety. Similar boron reagents also underwent PET reaction with aromatic ketones by the 4th basic ligand to perform allylation and benzylation. These reactions are the first examples of allylation via PET using silicon and boron reagents. Alkytin reagents, which were not good reagents for PET, could be applied to the carbonyl alkylation by the substitution of an alkyl by a hetero atom. Furthermore, hypervalent (5-coordenated) alkyltin reagents exhibited high efficiency of alkylation.
On the other hand, the effect of Lewis acids to the PET reaction was also investigated. Addition of metal salts to ketones accelerated the PET from allylsilicon reagents. As another topic, metal ion inhibited PET from amino moiety in allyltin reagent and selectively promoted PET from allyltin moiety to undergo carbonyl allylation.
For comparison with photoreaction, thermal Lewis acid promoted reaction was investigated. Allyltins containing a hydroxyl and an amino group, which were not suitable for the thermal acidic reaction, were successfully applied to the photoallylation reaction. This shows a synthetic merit of the photoreaction. As an advantage of the thermal reaction, Lewis acids could control stereoselectivity in allylation reaction by their coordination mode.

Report

(4 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • Research Products

    (9 results)

All Other

All Publications (9 results)

  • [Publications] 西垣内 寛, 宅和 暁男: "Stereospecific formation of deuterated homoallyl alcohols by Lewis acid-promoted reactions of allyltin and allylsilicon reagents toward aldehydes"Tetrahedron Letters. 43. 3045-3047 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 西垣内 寛, 宅和 暁男: "Reversible stereo control in the Lewis acid promoted reaction of alkoxyaldehydes toward various allyltins"Tetrahedron Letters. 44. 1405-1408 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 宅和 暁男, 佐々木 貴久, 岩本 秀俊, 西垣内 寛: "Regioselective allylation of 1,2-naphthoquiness using photoaddition reaction with allylsilanes : synthesis of 3-allyl-1,2-naphthoquinones"Synthesis. 63-68 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Yutaka Nishigaichi.: "Stereospecific formation of deuterated homoallyl alcohols by Lewis acid-promoted reactions of allyltin and allylsilicon reagents toward aldehydes"Tetrahedron Letters. 43. 3045-3047 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Yutaka Nishigaichi.: "Reversible stereocontrol in the Lewis acid promoted reaction of alkoxyaldehydes toward various allyltins"Tetrahedron Letters. 44. 1405-1408 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A,Takuwa., T,Sasaki., H,Iwamoto., Y,Nishigaichi.: "Regioselective allylation of 1, 2-naphthoquinones using photoaddition reaction with allylsilanes: synthesis of 3-ally-1, 2-naphthoquinones"Synthesis. 63 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 西垣内 寛, 宅和 暁男: "Stereospecific formation of deuterated homoallyl alcohols by Lewis acid-promoted reactions of allyltin and allylsilicon reagents toward aldehydes"Tetrahedron Letters. 43. 3045-3047 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 西垣内 寛, 宅和 暁男: "Reversible stereocontrol in the Lewis acid promoted reaction of alkoxyaldehydes toward various allyltins"Tetrahedron Letters. 44. 1405-1408 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] 西垣内 寛, 宅和 暁男: "Stereospecific formation of deuterated homoallyl alcohols by Lewis acid-promoted reactions of allyltin and allylsilicon reagents toward aldehydes"Tetrahedron Letters. 43巻(発表予定). (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2000-04-01   Modified: 2016-04-21  

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