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1987 Fiscal Year Final Research Report Summary

Chemistry and Synthetid Applications of Reactive Species Generated by Redox and Related Reactions of Organometallic Compounds

Research Project

Project/Area Number 60470090
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionUniversity of Osaka Prefecture

Principal Investigator

OTSUJI Yoshio  Dept. of Applied Chem., Univ. of Osaka Prefecture, Professor, 工学部, 教授 (20081341)

Co-Investigator(Kenkyū-buntansha) MIZUNO Kazuhiko  Dept. of Applied Chem., Univ. of Osaka Prefecture, Assistant Prof., 工学部, 助手 (10109879)
NAKANISHI Saburo  Dept. of Applied Chem., Univ. of Osaka Prefecture, Assistant Prof., 工学部, 助手 (40081343)
ISAGAWA Kakuzo  Dept. of Applied Chem., Univ. of Osaka Prefecture, Associate Prof., 工学部, 助教授 (30081342)
Project Period (FY) 1985 – 1987
KeywordsGroup 14(group 4B) organometallic compounds / Low-valent titanium complexes / Iron carbonyl complexes / (<eta>^3-Allylic)nitrosyl iron complexes / Photoinduced electron-transfer / Three-component coupling reactions / Hydroboration / 還元的脱酸素反応
Research Abstract

The titled subject have been investigated and the following results have been obtained.
1. Novel reactions such as the substitution of CN group in dicyanoaromatics by allylic and benzylic groups, the addition of these groups to dicyanoaromatics and dicyanoalkenes, the oxidative cleavage of group 14 organometallics, and the double C-C bond-forming reactions of electron-deficient alkenes were developed by studying the photoinduced electron-transfer from the group 14 organometallics to the dicyano compounds and Cu(II) ions, and also by studying the reactions of the electron-deficient alkenes with allylic stannanes in the presence of organoiodo compounds.
2. The regio- and stereo-selective hydroboration of alkadienes, allylic alcohols, and oxygen-containing unsaturated compounds were developed by use of lowvalent Ti-complexes as a catalyst.
3. New reactions such as the reductive deoxygenation of N-acyloxyimino compounds, the triple CO insertion to carbanions, the electrophilic and nucleophilic reactions on allylic compounds and <alpha><beta>-unsaturated carbonyl compounds via iron carbonyl complexes and (<eta>^3-allylic)Fe(CO)_2NO complexes.
4. The mechanistic features and synthetic applications of the above reactions, and also the reactivities of the reactive species involved were described.

  • Research Products

    (21 results)

All Other

All Publications (21 results)

  • [Publications] Kazuhiko Mizuno: Tetrahedron Letters. 26. 461-464 (1985)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuhiko Mizuno: Tetrahedron Letters. 26. 5819-5822 (1985)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 水野一彦: 有機合成化学協会誌. 44. 1010-1021 (1986)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 大辻吉男: 旭硝子工業技術奨励会研究報告. 49. 215-223 (1986)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuhiko Mizuno: Chemistry Letters. 203-204 (1987)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 水野一彦: 日本化学会誌. 1183-1188 (1987)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuhiko,Mizuno: "A Novel Photosubstitution of Dicyanobenzenes by Allylic and Benzylic Silanes" Tetrahedron Letters. 26. 461-464 (1985)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuhiko,Mizuno: "Regioselectrive Photoallylations of Dicyanopolycyclic Aromatic Compounds Via Electron Transfer" Tetrahedron Letters. 26. 5819-5822 (1985)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuhiko,Mizuno: "Chemistry of Photochemically Generated Reactive Species and Their Synthetic Applications" Yuki Gosei Kagaku Kyokai Shi. 44. 1010-1021 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yoshio,Otsuji: "Development and Applications of Highly Selective Organic Photoreactions via Photoinduced Electron Transfer" Reports of the Asahi Glass Foundation for Industrial Technology. 49. 215-223 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuhiko,Mizuno: "Regioselective Photoallylation of Furyl and Thienly Dicyanoethenes by Allylic Stannanes via Photoinduced Electron Transfer" Chemistry Letrers. 203-204 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuhiko,Mizuno: "Photoaddition of Allylic and Benzylic Groups to 1,1-Dicyanoethenesb Bearing Heterocyclic Substituents by Use of Organic Stannanes" Nippon Kagaku Kaishi. 1183-1188 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuhiko,Mizuno: "Photoallylation of 1,4-Dicyanonaphthalene by Use of Group 14 Organometallic Compounds" Chemistry Letters. 145-148 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuhiko,Mizuno: "Generation of Organic Cation from Group 14 Organometallic Compounds via Photoinduced Electron Transfer in the Presence of a(II) Salt" Chemistry Letters. 229-232 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuhiko,Mizuno: "Regioselective Double Vicinal Carbon-Carbon Bond Forming Reactions of Electron-Deficient Alkenes by Use of Allylic Stannanes and Organoiodo Compounds" Journal of the American Chemical Society. 110. 1288-1290 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuhiko,Mizuno: "Dual Regioselectivity in the Photoallylation of Electron Deficient Alkenes by Allylic Selanes" Journal of the American Chemical Society; Submitted for publication.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kakuzo,Isagawa: "Titanium Complex-Catalyzed Hydroboration of Oxygen-Containing Unsaturated Compounds" Bulletin of the Chemical Society of Japan in preparation.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Tatsuo,Ueda: "Preparation and Reactions of (<eta>^3-Allyl)dicarbonylnitrosyliron Complexes" Nippon Kagaku Kaishi. 271-281 (1985)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Tatsuo,Ueda: "Cyclodimerization of Benzylideneacetophenone and Its Derivatives by Use of Triiron Dodecacarbonyl" Chemistry Letters. 1631-1634 (1986)

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  • [Publications] Tatsuo,Ueda: "Cyclodimerization of Alkyl Styryl Ketones and Their Silyl Enol Ethers by Use of Iron Carbonyls" Chemisry Letters. 1635-1638 (1986)

    • Description
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  • [Publications] Keiji,Ito: "1-Trimethylsiloxyallylic Iron Complexes as a <beta>-Acylcarbanion Equivalent" Chemistry Letters. 2103-2106 (1987)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1989-03-30  

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