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2005 Fiscal Year Final Research Report Summary

Development of New Catalytic Asymmetric Reactions Based on the Synthesis of Optically Active Phosphine Ligands

Research Project

Project/Area Number 16350020
Research Category

Grant-in-Aid for Scientific Research (B)

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

Principal Investigator

IMAMOTO Tsuneo  Chiba University, Faculty of Science, Professor, 理学部, 教授 (10134347)

Co-Investigator(Kenkyū-buntansha) YOSHIDA Kazuhiro  Chiba University, Faculty of Science, Research Associate, 理学部, 助手 (60375607)
Project Period (FY) 2004 – 2005
KeywordsAsymmetric Hydrogenation / Optically Active Phosphine / Iridium Complex / Rhodium Complex / Phosphine / P-Chiral Phosphine / Chiral Ligands / Asymmetric Catalysis
Research Abstract

This study is directed toward the development of new catalytic asymmetric reactions based on the design and synthesis of novel chiral phosphine ligands. A new tetraphosphine ligand bearing their four chiral centers at phosphorus atoms has been synthesized via phosphine-boranes as the intermediates and the molecular structure of its dirhodium complex was determined by the single crystal X-ray analysis. The tetraphosphine lidand itself is C_2 symmetric, but each Rh-diphosphine sphere forms a C_1 symmetric three-hindered quadrant. This dirhodium complex exhibited excellent enantioinduction ability in Rh-catalyzed asymmetric hydrogenation of dehydroamino acids. Low temperature hydrogenation of the complex afforded a tetrahydrorhodium complex quantitatively, and the reactions of the tetrahydride complex with alkene substrates were studied in order to elucidate the detailed enantioselection mechanism. The results including the stereochemical outcome are reasonably interpreted by assuming tha … More t the enantioselection would be determined at the migratory insertion step.
A new P-chiral phosphinophenol was prepared and employed in copper-catalyzed asymmetric conjugate addition to α,β-unsaturated carbonyl compounds. The reactions proceeded smoothly under mild conditions to afford the corresponding products with high enantiomeric excesses of up to 96%.
Asymmetric hydrosilylation of simple ketones was tested by the use of several P-chiral phosphine ligands prepared in our laboratory. Very high enantioselectivity of up to 99% was observed when a bulky silylation reagent such as α-naphtyldiphenylsilane was used. The sense of the stereoselection has been rationalized by considering that the enantioselection occurs at the migratory insertion step.
A new P-chiral diphosphine ligand, (R,R)-2,3-bis(tert-butylmethylphosphino)quinoxaline (QuinoxP^*)) was designed and synthesized by reacting enantiomerically pure (R)-tert-butyl(hydroxymethyl)methylphosphine-borane with 2,3-dichloroquinoxaline. This ligand, in contrast to most of the previously reported P-chiral ligands, is an air-stable solid and exhibits excellent enantioselectivities in both Rh-catalyzed asymmetric hydrogenations and Rh- or Pd-catalyzed carbon-carbon bond-forming reactions. Less

  • Research Products

    (31 results)

All 2006 2005 2004

All Journal Article (30 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] P-Chiral Tetraphosphine Dirhodium Complex as a Catalyst for Asymmetric Hydrogenation : Synthesis, Structure,Enantioselectivity,and Mechanism. Stereoselective Formation of a Derhodium Tetrahybride Complex and Its Reaction with Methyl(Z)-α-Acetamidocinnamate2006

    • Author(s)
      T.Imamoto, K.Yashio, K.V.L.Crepy, H.Takahashi, M.Mouichi, I.D.Gridnev
    • Journal Title

      Organometalllcs 25

      Pages: 908-914

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Highly Enantioselective Hydrosilylation of Simple Ketones Catalyzed by Rhodium Complexes of P-Chiral Diphosphine Ligands Bearing tert-Butylmethylphosphino Group.2006

    • Author(s)
      T.Imamoto, T.Ito, Y.Yamanoi, R.Narui, K.Yoshida
    • Journal Title

      Tetrahedron : Asymmetry 17

      Pages: 560-565

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Enantioselective Hydrogenation of Acyclic Aromatic N-Aryl Iminess Catalyzed by an Iridium Complex of(S,S)-1,2-Bis(tert-butylmethylphosphino)ethane2006

    • Author(s)
      T.Imamoto, N.Iwadate, K.Yoshida
    • Journal Title

      Organic Letters 8

      Pages: 2289-2292

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] P-Chiral Tetraphosphine Dirhodium Complex as a Catalyst for Asymmetric Hydrogenation : Synthesis, Structure, Enantioselectivity, and Mechanism. Stereoselective Formation of a Dirhodium Tetrahydride Complex and Its Reaction with Methyl (Z)-α-Acetamidocinnamate,2006

    • Author(s)
      Imamoto, T., Yashio, K., Crepy, K.V.L., Katagiri, K., Takahashi, H., Kouchi, M., Gridnev, I.D.
    • Journal Title

      Organometallics 25

      Pages: 908-914

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Highly Enantioselective Hydrosilylation of Simple Ketones Catalyzed by Rhodium Complexes of P-Chiral Diphosphine Ligands Bearing tert-Butylmethyrphosphino Groups,2006

    • Author(s)
      Imamoto, T., Itoh, T., Yamanoi, Y., Narui, R., Yoshida, K.
    • Journal Title

      Tetrahedron : Asymmetry 17

      Pages: 560-565

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Enantioselective Hydrogenation of Acyclic Aromatic N-Aiyl Imines Catalyzed by an Iridium Complex of (S,S)-1,2-Bis(tert-butylmethylphosphino)ethane,2006

    • Author(s)
      Imamoto, T., Iwadate, N., Yoshida, K.
    • Journal Title

      Org.Lett. 8

      Pages: 2289-2292

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Nucleophilic Aromatic Substitution Reactions of Fluorobenzenechromium Complexes with P-Chiral Secondary Phosphine-Boranes : Synthesis of Optically Pure P-Chiral (Dialkyl)arylphosphine-Boranes2005

    • Author(s)
      K.Katagiri, H.Danjo, K.Yamaguchi, T.Imamoto
    • Journal Title

      Tetrahedron 61

      Pages: 4701-4704

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Preparation of (S,S)-1,2-Bis(tert-butylmethylphosphino)ethane as a Rhodium Complex2005

    • Author(s)
      K.V.L.Crepy, T.Imamoto, G.Seidel.A.Furstner
    • Journal Title

      Organic Syntheses 82

      Pages: 22-29

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Evidence for the importance of conformational equilibria in Rh-diphosphine complexes for the enantioselection in Rh-catalyzed asymmetric hydrogenation2005

    • Author(s)
      H.Tsuruta, T.Imamoto, K.Yamaguchi, I.D.Gridnev
    • Journal Title

      Tetrahedron Letters 46

      Pages: 2879-2882

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] An Air-stable P-chiral Phosphine Ligand for Higyly Enantioselective Transition-Metal-Catalyzed Reactions2005

    • Author(s)
      T.Imamoto, K.Sugita, K.Yoshida
    • Journal Title

      Journal of the American Chemical Society 127

      Pages: 11934-11935

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] P-Chiral o-Phosphinophenol as a P/O Hybrid Ligand : Preparation and Use in Cu-Catalyzed Asymmetric Conjugate Addition of Diethylzinc to Acyclic Enones2005

    • Author(s)
      Y.Takahashi, Y.Yamamoto, K.Katagiri, H.Danjo, K.Yamaguchi, T.Imamoto
    • Journal Title

      Journal of Organic Chemistry 70

      Pages: 9009-9012

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] An Air-Stable P-Chiral Phosphine Ligands for Highly Enantioselective Transition-Metal-Catalyzed Reactions,2005

    • Author(s)
      Imamoto, T., Sugita, K., Yoshida, K.
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 11934-11935

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] P-Chiral o-Phosphinophenol as a P/O Hybrid Ligand : Preparation and Use in Cu-Catalyzed Asymmetric Conjugate Addition of Diethylzinc to Acyclic Enones,2005

    • Author(s)
      Takahashi, Y., Yamamoto, Y., Katagiri, K., Danjo, K., Yamaguchi, K., Imamoto, T.
    • Journal Title

      J.Org.Chem. 70

      Pages: 9009-9012

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Evidence for the Importance of Conformational Equilibria in Rh-Diphosphine Complexes for the Enantioselection in Rh-Catalyzed Asymmetric Hydrogenation,2005

    • Author(s)
      Tsuruta, H., Imamoto, T., Yamaguchi, K., Gridnev, I.D.
    • Journal Title

      Tetrahedron Lett. 46

      Pages: 2879-2882

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Nucleophilic Aromatic Substitution Reactions of Fluorobenzenechromium Complexes with P-Chiral Secondary Phosphine-Boranes : Synthesis of Optically Pure P-Chiral (Dialkyl)arylphosphine-Boranes,2005

    • Author(s)
      Katagiri, K., Danjo, D., Yamaguchi, K., Imamoto, T.
    • Journal Title

      Tetrahedron 61

      Pages: 4701-4704

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Preparation of (S,S)-Bis(tert-butylmethylphosphino)ethane ((S,S)-t-Bu-BisP^*) as a Rhodium Complex,.2005

    • Author(s)
      Crepy, K.V.L., Imamoto, T., Seidel, G., Furstner, A.
    • Journal Title

      Organic Syntheses 82

      Pages: 22-29

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Asymmetric Hydrogenation of α.,β-Unsaturated Phosphonates with Rh-BisP^* and Rh-MiniPHOS Catalysts : Scope and Mechanism of the Reaction.2004

    • Author(s)
      I.D.Gridnev, M.Yasutake, T.Imamoto, I.P.Beletskaya
    • Journal Title

      Proceedings of the National Academy of Sciences, USA 101

      Pages: 5385-5390

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] 1,1'-Di-tert-2,2'-dibenzo-phosphetanyl : A Highly Straned P-Stereogenic Diphosphine Ligands.2004

    • Author(s)
      T.Imamoto, K.V.L.Crepy, K.Katagiri
    • Journal Title

      Tetrahedron : Asymmetry 15

      Pages: 2213-2218

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] P-Stereogenic P/N Hybrid Ligands : A Remarkable Switch in Enantioselectivity in Palladoum-Catalyzed asymmetric Allylation.2004

    • Author(s)
      H.Danjo, M.Higuchi, M.Yada, T.Imamoto
    • Journal Title

      Tetrahedron Letters 45

      Pages: 603-606

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] On the Mechanism of Stereoselection in Rh-Catalyzed asymmetric Hydrogenation : A General Approach for Predicting the Sense of Enantioselectivity.2004

    • Author(s)
      I.D.Gridnev, T.Imamoto
    • Journal Title

      Accounts of Chemical Researches 37

      Pages: 633-644

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Diliydroboronium Derivatives of (S,S)-1,2-Bis(t-butylmethylphosphino) ethane as Convenient Chiral Ligand Precursors.2004

    • Author(s)
      T.Miyazaki, M.Sugawara, H.Danjo, T.Imamoto
    • Journal Title

      Tetrahedron Letters 45

      Pages: 9341-9344

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Optically Pure 1,2-[Bis(o-alkylphenyl) phenylphosphino]ethanes and Their Use in Rhodium-Catalyzed Asymmetric Hydrogenations of a-(Acylanilno) acrylic Derivatives.2004

    • Author(s)
      Y.Wada1, T.Imamoto, H.Tsuruta, K.Yamaguchi, I.D.Gridnev
    • Journal Title

      Advanced Synthesis & Catalysis 346

      Pages: 777-788

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Optically Active Di-tert-buty-1-2,2'-diphosphetanyland Its Application in Rhodium-Catalyzed asymmetric Hydrogenations.2004

    • Author(s)
      T.Imamoto, N.Oohara, H.Takahashi
    • Journal Title

      Synthesis 2004

      Pages: 1353-1358

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Asymmetric Hydrogenation of α,β-Unsatirated Phosphonates with Rh-BisP^* and Rh-MiniPHOS Catalysts : Scope and Mechanism of the Reaction2004

    • Author(s)
      Gridnev, I.D., Yasutake, M., Imamoto, T., Beletskaya, I.P.
    • Journal Title

      Proc.Natl.Acad.Sci.USA 101

      Pages: 5385-5390

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Optically Active 1.1'-Di-tert-2,2'-dibenzo-phosphetanyl : A Highly Strained P-Stereogenic Diphosphine Ligands2004

    • Author(s)
      Imamoto, T., Crepy, K.V.L., Katagiri, K.
    • Journal Title

      Tetrahedron : Asymmetry 15(Special Issue)

      Pages: 2213-2218

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] P-Stereogenic P/N Hybrid Ligands : A Remaxkable Switch in Enantioselectivity in Palladium-Catalyzed Asymmetric Allylation,2004

    • Author(s)
      Danjo, H., Higuchi, M., Yada, M., Imamoto, T.
    • Journal Title

      Tetrahedron Lett. 45

      Pages: 603-606

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] On the Mechanism of Stereoselection in Rh-Catalyzed Asymmetric hydrogenation : A General Approach for Predicting the Sense of Enantioselectivity,2004

    • Author(s)
      Gridnev, I.D., Imamoto, T.
    • Journal Title

      Acc.Chem.Res. 37

      Pages: 633-644

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Dihydroboronium Derivative of (S,S)-1,2-Bis(t-butylmethylphosphino)ethane as Convenient Chiral Ligand Precursors,2004

    • Author(s)
      Miyazaki, T., Sugawara, M., Danjo, H., Imamoto, T.
    • Journal Title

      Tetrahedron Lett. 45

      Pages: 9341-9344

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Optically Pure 1,2-[Bis(o-alkylphenyl)phenylphosphino]ethanes and Their Use in Rhodium-Catalyzed Asymmetric Hydrogenations of α-(Acylamino)acrylic Derivatives,2004

    • Author(s)
      Wada, Y., Imamoto, T., Tsuruta, H., Yamaguchi, K., Gridnev, I.D.
    • Journal Title

      Adv.Syn.Catal. 346

      Pages: 777-788

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Optically Active Di-tert-butyl-2,2'-diphosphetanyl and Its Application in Rhodium-Catalyzed Asymmetric Hydrogenations,2004

    • Author(s)
      Imamoto, T., Oohara, N., Takahashi, H.
    • Journal Title

      Synthesis (Special Issue)

      Pages: 1353-1358

    • Description
      「研究成果報告書概要(欧文)」より
  • [Patent(Industrial Property Rights)] 2,3- ビス(ジアノレキノレホスフィノ)ピラジン誘導体及びその製造方法2005

    • Inventor(s)
      今本恒雄, 吉田和弘, 杉田敬太郎
    • Industrial Property Rights Holder
      千葉大学日本科学工業((株))
    • Industrial Property Number
      特願2005-215003
    • Filing Date
      2005-07-25
    • Description
      「研究成果報告書概要(和文)」より

URL: 

Published: 2007-12-13  

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