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Enantioselective Hydrogenation of Ketones

Research Project

Project/Area Number 11440188
Research Category

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

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

Principal Investigator

OHKUMA Takeshi  Nagoya University, Graduate School of Sciences, Associate Professor, 大学院・理学研究科, 助教授 (50201968)

Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥13,600,000 (Direct Cost: ¥13,600,000)
Fiscal Year 2000: ¥6,300,000 (Direct Cost: ¥6,300,000)
Fiscal Year 1999: ¥7,300,000 (Direct Cost: ¥7,300,000)
Keywordsasymmetric hydrogenation / BINAPs / carbonyl-selective hydrogenation / chiral alcohols / chiral Ru (II) complexes / 1, 2-diamine / enantioselectivity / ketones / ベンゾフェノン類 / 複素環 / カルボニル選択性
Research Abstract

The development of practical methods effecting stereoselective hydrogenation of simple ketones is highly desirable, since the existing homogeneous catalysts lack reactivity and/or stereoselectivity. A new Ru (II) complex, trans-RuCl_2 [(S)-xylbinap][(S)-daipen] or the R, R enantiomer acts as an excellent precatalyst for asymmetric hydrogenation of simple ketones (XylBINAP=2, 2'-bis (di-3, 5-xylylphosphino)-1, 1'-binaphthyl. DAIPEN=1, 1-dianisyl-2-isopropyl-1, 2-ethylenediamine). The reaction is conducted with a substrate/catalyst molar ratio of up to 100000 in 2-propanol containing alkaline base under 1-80 atm (mostly <10 atm) of H_2 at room temperature. A wide variety of prochiral ketones are hydrogenated with a high degree of enantioselection. Hydrogenation of open-chain α, β-unsaturated ketones proceeds selectively at the C=O linkage to afford chiral allylic alcohols with a high ee, solving a long-standing synthetic problem. Hydrogenation of cyclopropyl ketones gives the correspondi … More ng carbinols in high ee without skeletal change. Alkyl aryl ketones with various substituents are hydrogenated with a consistently high enantioselectivity. 2, 2, 2-Trifluoroacetophenone and the ring-substituted derivatives are also usable as substrates. The reaction is tolerant of aromatic halides and CF_3, OCH_2, COOCH(CH_3)_2, NO_2, and NH_2 groups. Various ortho-substituted benzophenones are hydrogenated to chiral benzhydrols with consistently high ee. No over-reduction forming to diarylmethanes are observed. The catalyst system is extremely effective for enantioselective hydrogenation of hetero-aromatic ketones. The substrates with furan, thiophene, pyrrole, thiazole, or pyridine rings are hydrogenated with the same asymmetric sense to give chiral secondary alcohols in consistently high ee. The electronic properties, Lewis basic tendency, and steric size of the heterocycles appear to have little effect on the extent of enantioselectivity. This procedure is particularly useful for a large-scale reaction because of the low cost of the catalyst, operational simplicity, and environmental consciousness. Less

Report

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

    (51 results)

All Other

All Publications (51 results)

  • [Publications] T.Ohkuma: "Asymmetric Hydrogenation of Alkenyl, Cyclopropyl, and Aryl Ketones. RuCl_2(xylbinap)(1,2-diamine) as a Precatalyst Exhibiting a Wide Scope."J.Am.Chem.Soc.. 120・51. 13529-13530 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Mikami: "Conformationally Flexible Biphenylphosphane Ligands for Ru-Catalyzed Enantioselective Hydrogenation."Angew.Chem.Int.Ed.. 38・4. 495-497 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] M.Watanabe: "Enantioresolution by the Chiral Phthalic Acid method : Absolute Configuration of (2-Methoxyphenyl) phenylmethanol and Related Compounds."Tetrahedron : Asymmetry. 10. 2075-2078 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] R.Noyori: "Rapid, Productive and Stereoselective Hydrogenation of Ketones."Pure Appl.Chem.. 71・8. 1493-1501 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 大熊毅: "単純ケトン類の高速かつ高立体選択的水素化反応"有機合成化学協会誌. 57・8. 667-676 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "Selective Hydrogenation of Benzophenones to Benzhydrols.Asymmetric Synthesis of Unsymmetrical Diarylmethanols."Org.Lett.. 2・5. 659-662 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "General Asymmetric Hydrogenation of Hetero-aromatic Ketones."Org.Lett.. 2・12. 1749-1751 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "Asymmetric Hydrogenation of Amino Ketones Using Chiral RuCl_2(diphosphine)(1,2-diamine) Complexes."J.Am.Chem.Soc.. 122・27. 6510-6511 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Kuwahara: "Enantioresolution and Absolute Stereochemistry of o-Substituted Diphenylethanol."J.Am.Chem.Soc.. 5. 109-114 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Mikami: "Asymmetric Activation/Deactivation of Racemic Ru Catalysts for Highly Enantioselective Hydrogenation of Ketonic Substrates."Angew.Chem.Int.Ed.. 39・20. 495-497 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] G.S.Forman: "Asymmetric Hydrogenation of α-Ethylstyrenes Catalyzed by Chiral Ruthenium Complexes."Tetrahedron Lett.. 41・49. 9471-9475 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] R.Noyori: "Asymmetric Catalysis by Architectural and Functional Molecular Engineering : Practical Chemo-and Stereoselective Hydrogenation of Ketones."Angew.Chem.Int.Ed... 40・1. 40-73 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] R.Noyori: "Asymmetric Hydrogenation via Architectural and Functional Molecular Engineering."Pure Appl.Chem.. (in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 大熊毅: "これはすごい!化学の世界記録集(最も回転効率の高い分子触媒)"化学同人. 5 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "Comprehensive Asymmetric Synthesis(Hydrogenation of Carbonyl Group)"Springer. 48 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "Catalytic Asymmetric Synthesis, 2nd Ed(Asymmetric Hydrogenation)"Wiley-VCH. 110 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 大熊毅: "キラル医薬中間体のプロセス技術〜開発・製造とアウトソーシングの動向(不斉水素化)"技術情報協会(印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "Asymmetric Hydrogenation of Alkenyl, Cyclopropyl, and Aryl Ketones. RuCl_2 (xylbinap)(1, 2-diamine) as a Precatalyst Exhibiting a Wide Scope"J.Am.Chem.Soc.. 120 51. 13529-13530 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Mikami: "Conformationally Flexible Biphenylphosphane Ligands for Ru-Catalyzed Enantioselective Hydrogenation"Angew.Chem.Int.Ed.. 38 4. 495-497 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] M.Watanabe: "Enantioresolution by the Chiral Phthalic Acid Method : Absolute Configuration of (2-Methoxyphenyl) phenylmethanol and Related Compounds"Tetrahedron : Asymmetry. 10. 2075-2078 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] R.Noyori: "Rapid, Productive and Stereoselective Hydrogenation of Ketones"Pure Appl.Chem.. 71 8. 1493-1501 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "High-Speed and Highly Stereoselective Hydrogenotion of Simple Ketones"J.Synth.Org.Chem.Jpn.. 57 8. 667-676 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "Selective Hydrogenation of Benzophenones to Benzhydrols. Asymmetric Synthesis of Unsymmetrical Diarylmethanols"Org.Lett.. 2 5. 659-662 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "General Asymmetric Hydrogenation of Hetero-aromatic Ketones"Org.Lett.. 2 12. 1749-1751 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "Asymmetric Hydrogenation of Amino Ketones Using Chiral RuCl_2 (diphosphine)(1, 2-diamine) Complexes"J.Am.Chem.Soc.. 122 27. 6510-6511 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Kuwahara: "Enantioresolution and Absolute Stereochemistry of o-Substituted Diphenylethanol"Enantiomer. 5. 109-114 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Mikami: "Asymmetric Activation/Deactivation of Racemic Ru Catalysts for Highly Enantioselective Hydrogenation of Ketonic Substrates"Angew.Chem.Int.Ed.. 39 20. 495-497 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] G.S.Forman: "Asymmetric Hydrogenation of α-Ethylstyrenes Catalyzed by Chiral Ruthenium Complexes"Tetrahedron Lett.. 41 49. 9471-9475 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] R.Noyori: "Asymmetric Catalysis by Architectural and Functional Molecular Engineering : Practical Chemo- and Stereoselective Hydrogenation of Ketones"Angew.Chem.Int.Ed.. 40 1. 40-73 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] R.Noyori: "Asymmetric Hydrogenation via Architectural and Functional Molecular Engineering"Pure Appl.Chem.. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "The Most Active Molecular Catalyst "Champion Data in Chemistry""Kagaku Dojin. 111-115 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "Hydrogenation of Carbonyl Groups "Comprehensive Asymmetric Synthesis, " ed. by E.N.Jacobsen, A.Pfaltz, and H.Yamamoto"Springer, Berlin Vol.1. 119-246 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "Asymmetric Hydrogenation "Catalytic Asymmetric Synthesis." 2nd Ed., ed. by I.Ojima"Wiley-VCH, New York. 1-110 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "Asymmetric Hydrogenation "Synthesis of Chiral Drug Intermediates, " ed. by I.Shinkai"Johogijutsukyokai (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Ohkuma: "Selective Hydrogenation of Benzophenones to Benzhydrols. Asymmetric Synthesis of Unsymmetrical Diarylmethanols."Org.Lett.. 2・5. 659-662 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Ohkuma: "General Asymmetric Hydrogenation of Hetero-aromatic Ketones."Org.Lett.. 2・12. 1749-1751 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Ohkuma: "Asymmetric Hydrogenation of Amino Ketones Using Chiral RuCl_2 (diphosphine)(1,2-diamine) Complexes."J.Am.Chem.Soc.. 122・27. 6510-6511 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Kuwahara: "Enantioresolution and Absolute Stereochemistry of o-Substituted Diphenylethanol."Enantiomer. 5. 109-114 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Mikami: "Asymmetric Activation/Deactivation of Racemic Ru Catalysts for Highly Enantioselective Hydrogenation of Ketonic Substrates."Angew.Chem.Int.Ed.. 39・20. 495-497 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] G.S.Forman: "Asymmetric Hydrogenation of α-Ethylstyrenes Catalyzed by Chiral Ruthenium Complexes."Tetrahedron Lett.. 41・49. 9471-9475 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] R.Noyori: "Asymmetric Catalysis by Architectural and Functional Molecular Engineering : Practical Chemo- and Stereoselective Hydrogenation of Ketones."Angew.Chem.Int.Ed.. 40・1. 40-73 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] R.Noyori: "Asymmetric Hydrogenation via Architectural and Functional Molecular Engineering."Pure Appl.Chem.. (in press).

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Ohkuma: "Catalytic Asymmetric Synthesis, 2nd Ed (Asymmetric Hydrogenation)"Wiley-VCH. 110 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 大熊毅: "キラル医薬中間体のプロセス技術〜開発・製造とアウトソーシングの動向(不斉水素化)"技術情報協会(印刷中).

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Mikami: "Conformationally Flexible Biphenylphosphane Ligands for Ru-Catalyzed Enantioselective Hydrogenation"Angew. Chem. Int. Ed.. 38・4. 495-497 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] M.Watanabe: "Enantioresolution by the Chiral Phthalic Acid Method"Tetrahedron: Asymmetry. 10. 2075-2078 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Ohkuma: "Rate Acceleration in Nucleophilic Alkylation of Carbonyl Compounds with a New Template Containing Two Metallic Centers"Chemtracts-Org. Chem.. 12. 526-531 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T. Ohkuma: "Selective Hydrogenation of Benzophenones to Benzhydrols. Asymmetric Synthesis of Unsymmetrical Diarylmethanols"Org. Lett.. (in press).

    • Related Report
      1999 Annual Research Report
  • [Publications] 大熊 毅: "単純ケトン類の高速かつ高立体選択的水素化反応"有機合成化学協会誌. 57・8. 667-676 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Ohkuma: "Comprehensive Asymmetric Synghesis"Springer. 48 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 大熊 毅: "これはすごい!化学の世界記録集"化学同人. 5 (1999)

    • Related Report
      1999 Annual Research Report

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

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