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Exploitation of New Catalytic Methods for the Construction of Carbon Frameworks and the Control of Reaction Fields

Research Project

Project/Area Number 63470073
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionToyohashi University of Technology

Principal Investigator

ITOH Kenji  Toyohashi University of Technology, Department of Materials Science, Professor., 工学部, 教授 (60023149)

Co-Investigator(Kenkyū-buntansha) NAGASHIMA Hideo  Toyohashi University of Technology, Department of Materials Science, Assistant., 工学部, 助手 (50159076)
Project Period (FY) 1988 – 1990
Project Status Completed (Fiscal Year 1990)
Budget Amount *help
¥6,400,000 (Direct Cost: ¥6,400,000)
Fiscal Year 1990: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1989: ¥2,600,000 (Direct Cost: ¥2,600,000)
Fiscal Year 1988: ¥2,800,000 (Direct Cost: ¥2,800,000)
KeywordsHomogeneous catalysis / Oligomerization of diens / Ruthenium complexes / carbon-carbon bond formation / Radical cyclization / Pyrrolidone derivatives / Lactone synthesis / Asymmetric synthesis / 炭素一炭素結合形成 / ラジカル還化反応 / 炭素-炭素結合形成 / ピロイドン誘導体 / ジエン・ルテニウム錯体 / ラジカル環化反応 / 炭素ー炭素結合形成 / 8員環構築法
Research Abstract

(1) There have been no systematic study on organoruthenium chemistry with high oxidation states until this project was started. Several new pi-allyl ruthenium(IV) complexes bearing cyclopentadinyl(Cp) or pentamethylcyclopentadienyl(Cp^*) ligands were successfully prepared in this project for the first time. The X-ray structure determination of the representative Cp^*Ru(pi-allyl)Br_2 was undertaken. Several important aspects on the chemical reactivity of the carbon-ruthenium(IV) bonds in these new organoruthenium(IV) compounds were investigated in detail. Judicious combinations of the elemental organometallic reactions provide new highly selective catalyses based on Ru(II)-Ru(IV) redox channel. Linear oligomerization of butadiene or 1,3-pentadiene proceeds with "CpRu^+" or "Cp^*Ru^+" type catalysts. Furthermore, a cyclic dimerization of butadiene or isoprene was found to take place under mild condition to give the corresponding eight-membered carbocyclic frameworks with extremely high r … More egio- and stereo-selectivity by means of "Cp^*Ru^+" catalyst. A reasonable mechanism was elucidated based on a number of stoichiometric model reactions between Cp^*RuX(diene)/AgOTf and the conjugated dienes.
(2) Single electron transfer from Cu(I) or Ru(II) complexes was found to be extremely effective redox channel to the intramolecular radical addition to form C-C bonds. This original concept makes stoichiometric radical cyclizations to homogeneous catalytic processes. New catalytic radical cyclization was exploited for the construction of trichlorinated gamma-lactam or lactone skeletons starting from the appropriate acyclic precursors such as N-allyltrichloroacetamide or allyltrichloroacetate derivatives. These new methodologies were extended to some sequential multi-step radical cyclization, and to the asymmetric induction at the geminal carbon atoms on the lactam or lactone skeletons.
(3) Completely novel chiral auxiliary, bis(oxazolinyl)pyridine, was designed and successfully synthesized. Its rhodium(III) complex provides a terdentate meridional C_2-chiral reaction field for enantioselective catalysis. Less

Report

(4 results)
  • 1990 Annual Research Report   Final Research Report Summary
  • 1989 Annual Research Report
  • 1988 Annual Research Report
  • Research Products

    (30 results)

All Other

All Publications (30 results)

  • [Publications] Nagashima,Hideo: "Oxidative Addition of Allylic Halides to Ruthenium(II) Compounds: Preparation, Reactions and Xーray Crystallographic Structure of Ruthenium(IV) Allyl Complexes" Organometallics. 9. 799-807 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] 伊藤 健児: "有機ルテニウム錯体の炭素ー炭素結合生成反応" Organometallic News. 213-216 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] 伊藤 健児: "有機ルテニウム(IV)錯体の合成と反応" 日本化学会誌. (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Nagashima,Hideo: "Highly Stereoselective Radical Cyclization: Copper or Ruthenium Catalyzed Preparation of cisー and transーΒ,γーDialkyl γーLactams from Acyclic NーAllyltrichloroacetamide Derivatives" Journal of Organic Chemistry. 54. 4497-4499 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Nagashima,Hideo: "TransitionーMetal Catalyzed Radical Cyclization: CopperーCatalyzed Cyclization of Allyl Trichloroacetates to Trichlorinated γーLactones" Journal of Organic Chemistry. 55. 985-990 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Nagashima,Hideo: "Formation of Ru^<II>ーAlkylーButadiene Complexes from DihalogenoーRu^<IV>ーAllyl Precursors by the Reaction with BrMg(CH_2)_4MgBr: A Novel Decomposition Pathway for Ruthena(IV)cyclopentene Intermediates" Journal of Organometallic Chemistry. (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Nishiyama,Hisao: "Chiral and C2ーSymmetrical Bis(oxazolinyl)pyridinerhodium(III) Complexes: Effective Catalysts for Asymmetric Hydrosilylation of Ketones" Organometallics. 8. 846-848 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Nishiyama,Hisao: "Highly Enantioselective Hydrosilylation of Ketones with Chiral and C2ーSymmetrical Bis(oxazolinyl)pyridineーRhodium Catalyst" Organometallics. 10. 500-508 (1991)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Nagashima,Hideo: "Transition Metal Catalyzed Radical Cyclization: New Preparative Route to γーLactams from Allylic Alcohols via 3,3ーSigmatropic Rearrangement of Trichloroacetimidates" Journal of Organic Chemistry.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Nishiyama,Hisao: "2,6ーBis(4^'ー(S)ーisopropyloxazolinー2,7ーyl)ー4ーN,Nーdimethylaminoーpyridine as a Chiral Auxiliary for Catalytic Asymmetric Reduction of Ketones" Tetrahedron Letters.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Nagashima, Hideo ; Mukai, Katsunori ; Siota, Yusuke Yamaguchi, Keitaro ; Ara, Ken-ichi ; Fukahori, Takahiko, Suzuki, Hiroharu ; Akita, Munetaka ; Moro-oka, Yoshihifo ; Itoh, Kenji: "Oxidative Addition of Allylic Halides to Ruthenium(II) Compound : Preparation, Reactions, X-ray Crystallographic Structure of Ruthenium(IV)-Allyl Complexes" Organometallics. vol. 9,. 799-807 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Itoh, Kenji ; Nagashima, Hideo ; Fukahori, Takahiko: "Preparation and Reactions of Organoruthenium(IV) Complexes" Nippon Kagaku Kaishi. No. 3. (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Nagashima, Hideo ; Michino, Yoshiyuki ; Ara, Ken-icni, Fukahori, Takahiko ; Itoh, Kenji: "Formation of Ru^<11>-AlkylーButadiene Complexes from Dihalogeno-Ru^<1V>-Allyl Precursors by the Reaction with BrMg(CH_2)_4MgBr ; A Novel Decomposition Pathways for Ruthena(IV)cyclopentane Intermedicates" Journal of Organometallic Chemistry,. (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Nagashima, hideo ; Ozaki, Nobuyasu ; Seki, Koji ; Ishii, Masayuki ; Itoh, Kenji: "Highly Stereoselective Radical Cyclization : Copper or Ruthenium-Catalyzed Preparation of cic-and trans-beta, gamma-Dialkyl-gamma-Lactams from Acyclic N-Allyltrichloroacetamide Derivatives" Journal of Organic Chemistry. vol. 54. 4497-4499 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Nagashima, Hideo ; Seki, Koji ; Ozaki, Nobuyasu ; Wakamatu, Hidetoshi, Itoh, Kenji ; Tomo, Yoichi ; Tsuji, Jiro ;: "Transition-Metal-Catalyzed Radical Cyclization : Cyclization of Allyl Trichloroacetates to Trichlorinated gamma-Lactones" Journal of Organic Chemistry. vol. 55. 846-848 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Nishiyama, Hisao ; Sakaguchi, Hisao ; Nakamura, Takashi ; Horihata, Mihoko ; Kondo, Manabu ; Itoh, Kenji: "Chiral and C_2-Symmetrical Bis(oxazolinyl)-pyridine-rhodium Complexes ; Effective Catalysts for Asymmetric Hydrosilylation of Ketones" Organometallics. vol. 8. 846-848 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Nishiyama, Hisao ; Kondo, Manabu ; Nakamura, Takashi ; Itoh, Kenji: "Highly Enantioselective Hydrosilylation of Ketones with Chiral and C_2-Symmetrical Bis-(oxazolinyl)pyridine-Rhodium Catalysts" Organometallics. vol. 10. 500-508 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Nagashima,Hideo: "TransitionーMetalーCatalyzed Radical Cyclization:CopperーCatalyzed Cyclization of Allyl Trichloroacetates to Trichlorinated Lactones" Journal of Organic Chemistry. 55. 985-990 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Nagashima,Hideo: "Oxidative Addition of Allylic Halides to Ru(II) Compounds;Preparation,Reactions,and Xーray Crystallographic Structure of Ruthenium(IV)ーAllyl Complexes" Organometallics. 9. 799-807 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Nishiyama,Hisao: "Higyly Enantioselective Hydrosilylation of Ketones with Chiral and C2ーSymmetrical Bis(oxazolinyl)pyridineーRhodium Catalysts" Organometallics. 10. 500-508 (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] Nagashima,Hideo: "Formation of Ru^<ll>ーAlkylーButadiene Complexes from DihalogenoーRu^<lV>ーAllyl Precursors by the Reaction with BrMg(CH_2)_4MgBr:A Novel Decomposition Pathway for Ruthena(IV)cyclopentane Intermediates" Journal of Organometallic Chemistry. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] 伊藤 健児: "有機ルテニウム(IV)錯体の合成と反応" 日本化学会誌. (1991)

    • Related Report
      1990 Annual Research Report
  • [Publications] Hideo Nagashima: "Highly Stereoselective Radical Cyclization:Copper-or Ruthenium-Catalyzed Preparation of cis-and trans-B,γ-Dialkyl,γ-Lactams from Acyclic N-Allyltrichloroacetamide Derivatives." Journal of Organic Chemistry. 54. 4497-4499 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] Hideo Nagashima: "Transition-Metal-Catalyzed Radical Cyclization:Copper-Catalyzed Cyclization of Allyl Trichloroacetates to Trichlorinated γ-Lactones" Journal of Organic Chemistry. 55. 985-990 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] Hideo Nagashima: "Chiral and C_2-Symmetrical Bis(oxazolinylpyridine)rhodium(III)Complexes:Effective Catalysts for Asymmetric Hydrosilylation of Ketones." Organometallics. 8. 846-848 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] Hideo Nagashima: "(PPh_3)_3RhCl-Catalyzed Hydrosilylation of Unsaturated Molecules by 1,2-Bis(dimethylsilyl)ethane:Unprecedented Rate difference between Two Si-H Bonds." Organometallics. 8. 2495-2496 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] Hideo Nagashima: "Unprecedented 1,4-Methyl Gronp Migration in a Rhodium-catalysed Hydrosilylation of Ketones by 1,2-Bis(dimethylsilyl)benzene." Journal of Chemical Society,Perkin Transactions 1. 1707-1708 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] Hideo Nagashima: "Oxidative Addition of Allylic Halides to Ru(II)Compounds;Preparation,Reactions,and X-ray Crystallographic Structure of Ru(IV)-Allyl Complexes." Organometallics. 9. (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] Hideo Nagashima: Organometallics.

    • Related Report
      1988 Annual Research Report
  • [Publications] Hisao Nishiyama: Organometallics. 8. (1989)

    • Related Report
      1988 Annual Research Report

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Published: 1988-04-01   Modified: 2016-04-21  

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