• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Catalytic Asymetric Hydrogenation of Heteroaromatics

Research Project

Project/Area Number 11650891
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

KUWANO Ryoichi  Kyoto University, Graduate School of Engineering, Assistant Professor, 工学研究科, 助手 (20273477)

Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2000: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1999: ¥2,200,000 (Direct Cost: ¥2,200,000)
KeywordsCatalytic Asymmetric Synthesis / Chiral Phosphine / Asymmetric Hydrogenation / Indoline / Heteroaromatics / Indole / Rhodium / 光学活性ピラジン / 複素芳香環 / 水素化 / 光学活性化合物
Research Abstract

1. Catalytic Hydrogenation of Heteroaromatic Compounds using Transition Metal Complex
We found that rhodium complex generated from Rh (acac)(cod) and triphenylphosphine exhibited high catalytic activity for hydrogenation of indoles. The rhodium catalyst was also effective in hydrogenation of other 5-membered heteroaromatic compounds.
2. Catalytic Asymmetric Hydrogenation of 2-Substituted Indoles
The hydrogenation of N-acetyl-2-butylindole proceeded in the presence of cataionic (S, S)-(R,R)-PhTRAP-rhodium complex and cesium carbonate, giving (R)-N-acetyl-2-butylindoline with 94% ee in 92% isolated yield. This reaction is the first example of highly enantioselective hydrogenation of 5-membered heteroaromatic compounds. The chiral catalyst showed high enantioselectivity for the hydrogenation of other 2-substituted indoles (up to 95% ee).
3. Catalytic Asymmetric Hydrogenation of 3-Substituted Indoles
The chiral PhTRAP-rhodium catalyst exhibited good enantioselectivity (86% ee) for the hydrogenation of N-acetyl-3-methylindole, but the reaction was accompanied by serious alcoholysis of N-acetyl group. p-Toluenesulfonyl group is the protective group on nitrogen of choice in asymmetric hydrogenation of 3-substituted indoles. The hydrogenation of 3-methyl-N-p-toluenesulfonylindole gave the corresponding indoline with 98% ee in 93% isolated yield.

Report

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

    (26 results)

All Other

All Publications (26 results)

  • [Publications] Ryoichi Kuwano: "Synthesis of Trans-Chelating Chiral Diphosphine Ligand with Only Planar Chirality and Their Application to Asymmetric Hydrosilylation of Ketones"Tetrahedron Letters. 40. 1327-1330 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano: "Asymmetric Hydrogenation of 1,4;5,6-Tetrahydropyrazine-2-(N-tert-butyl)carboxamide Catalyzed by Trans-Chelating Chiral Diphosphine-Rhodium Complexes"The Journal of Organic Chemistry. 64. 1232-1237 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano: "Catalytic Asymmetric Allylation of Prochiral Nucleophiles, α-Acetamido-β-ketoesters"Journal of the American Chemical Society. 121. 3236-3237 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano: "Enantioselective Construction of Quaternary α-Carbon Centers on α-Amino Phosphonates via Catalytic Asymmetric Allylation"Organic Letters. 1. 837-839 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano: "Catalytic Asymmetric Hydrogenation of 1-Aza-2-cycloalkene-2-carboxylates Catalyzed by a Trans-Chelating Chiral Diphosphine PhTRAP-Rhodium Complex"Tetrahedron Letters. 40. 9045-9049 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano: "Asymmetric Hydrosilylation of Ketones Using Trans-Chelating Chiral Bisphosphine Ligands Bearing Primary Alkyl Substituents on Phosphorus Atoms"Bulletin of the Chemical Society of Japan. 73. 485-496 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano: "Hydrogenation of Five-Membered Heteroaromatic Compounds Catalyzed by a Rhodium-Phosphine Complex"Chemistry Letters. 428-429 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano: "Asymmetric Aldol Reaction of 2-Cyanopropionates Catalyzed by a Trans-Chelating Chiral Diphosphine-Rhodium(I) Complex : Highly Enantioselective Construction of Quaternary Chiral Carbon Centers at α-Positions of Nitriles"Journal of Organometallic Chemistry. 603. 18-29 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano: "Catalytic Asymmetric Hydrogenation of Heteroaromatic Compounds, Indoles"Journal of the American Chemical Society. 121. 7614-7615 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano: "Catalytic Asymmetric Hydrogenation of α-(Acetamido)acrylates Using TRAP Trans-Chelating Chiral Bisphosphine Ligands : Remarkable Effects of Ligand P-Substituent and Hydrogen Pressure on Enantioselectivity"Bulletin of the Chemical Society of Japan. 73. 2571-2578 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: "Synthesis of Trans-Chelating Chiral Diphosphine Ligand with Only Planar Chirality and Their Application to Asymmetric Hydrosilylation of Ketones"Tetrahedron Letters. 40. 1327-1330 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: "Asymmetric Hydrogenation of 1, 4, 5, 6-Tetrahydropyrazine-2-(N-tertbutyl) carboxamide Catalyzed by Trans-Chelating Chiral Diphosphine-Rhodium Complexes."The Journal of Organic Chemistry. 64. 1232-1237 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: "Catalytic Asymmetric Allylation of Prochiral Nucleophiles, α-Acetamido-β-ketoesters."Journal of the American Chemical Society. 121. 3236-3237 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: "Enantioselective Construction of Quaternary α-Carbon Centers on α-Amino Phosphonates via Catalytic Asymmetric Allylation"Organic Letters. 1. 837-839 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: "Catalytic Asymmetric Hydrogenation of 1-Aza-2-cycloalkene-2-carboxylates Catalyzed by a Trans-Chelating Chiral Diphosphine PhTRAP-Rhodium Complex"Tetrahedron Letters. 40. 9045-9049 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: "Asymmetric Hydrosilylation of Ketones Using Trans-Chelating Chiral Bisphosphine Ligands Bearing Primary Alkyl Substituents on Phosphorus Atoms"Bulletin of the Chemical Society of Japan. 73. 485-496 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: "Hydrogenation of Five-Membered Heteroaromatic Compounds Catalyzed by a Rhodium-Phosphine Complex"Chemistry Letters. 428-429 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: "Asymmetric Aldol Reaction of 2-Cyanopropionates Catalyzed by a Trans-Chelating Chiral Diphosphine-Rhodium (I) Complex : Highly Enantioselective Construction of Quaternary Chiral Carbon Centers at α-Positions of Nitriles"Journal of Organometallic Chemistry. 603. 18-29 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: "Catalytic Asymmetric Hydrogenation of Heteroaromatic Compounds, Indoles"Journal of the American Chemical Society. 121. 7614-7615 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano, et al.: "Catalytic Asymmetric Hydrogenation of α-(Acetamido) acrylates Using TRAP Trans-Chelating Chiral Bisphosphine Ligands : Remarkable Effects of Ligand P-Substituent and Hydrogen Pressure on Enantioselectivity"Bulletin of the Chemical Society of Japan. 73. 2571-2578 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoichi Kuwano: "Asymmetric Hydrosilylation of Ketones Using Trans-Chelating Chiral Bisphosphine Ligands Bearing Primary Alkyl Substituents on Phosphorus Atoms"Bulletin of the Chemical Society of Japan. 73. 485-496 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Ryoichi Kuwano: "Hydrogenation of Five-Membered Heteroaromatic Compounds Catalyzed by a Rhodium-Phosphine Complex"Chemistry Letters.. 428-429 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Ryoichi Kuwano: "Asymmetric Aldol Reaction of 2-Cyanopropionates Catalyzed by a Trans-Chelating Chiral Diphosphine-Rhodium (I) Complex : Highly Enantioselective Construction of Quaternary Chiral Carbon Centers at α-Positions of Nitriles"Journal of Organometallic Chemistry. 603. 18-29 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Ryoichi Kuwano: "Catalytic Asymmetric Hydrogenation of Heteroaromatic Compounds, Indoles"Journal of the American Chemical Society. 121. 7614-7615 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Ryoichi Kuwano: "Catalytic Asymmetric Hydrogenation of α-(Acetamido) acrylates Using TRAP Trans-Chelating Chiral Bisphosphine Ligands : Remarkable Effects of Ligand P-Substituent and Hydrogen Pressure on Enantioselectivity"Bulletin of the Chemical Society of Japan. 73. 2571-2578 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] R.Kuwano: "Hydrogenation of Five-Membered Heteroaromatic Compounds Catalyzed by Rhodium-Phosphine Complex"Chemistry Letters. (印刷中). (2000)

    • Related Report
      1999 Annual Research Report

URL: 

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

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi