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2008 Fiscal Year Annual Research Report

両親媒性高分子不斉触媒の創製

Research Project

Project/Area Number 19020025
Research InstitutionToyohashi University of Technology

Principal Investigator

伊津野 真一  Toyohashi University of Technology, 工学部, 教授 (50158755)

Keywords高分子固定化型触媒 / 両親媒性高分子 / 第四級アンモニウム塩 / 不斉アルキル化反応 / スルホン酸塩型高分子
Research Abstract

高分子固定化型触媒は、反応後の分離回収の容易さ、再使用の可能性、連続的なフローシステムの構築などの点から、効率的な有機合成プロセスのために重要な役割を果たしている。特に、貴重な遷移金属や、光学活性配位子などを利用する不斉反応では、容易にリサイクルが可能固定化触媒の使用が望まれる。一方で、環境負荷の軽減のため、有機溶媒の使用量を極力抑制し、水を媒体とした反応の開発はその重要性がさらに増している。不斉反応に関しても上記の要請に対して、不斉触媒の高分子固定化及び、水系での不斉反応の開発が必要とされている。しかしながら高分子固定化型不斉触媒を用いる水系での不斉反応についての成功例は少なく、重要な課題のひとつとなっている。そのために水系での有機反応に適切な反応場を提供できる両親媒性高分子の開発が必要である。本研究では高分子固定化と水系不斉反応の両者の組み合わせを目指して、両親媒性高分子およびそれを用いた高分子不斉触媒の開発に取り組んだ。特に第四級アンモニウム塩は、その合成の容易さ、幅広い構造の可能性、塩交換の容易さ、親水性-疎水性の程度を広範かつ詳細に制御できることなど優れた特徴を有していることから、この構造を取り入れた高分子固定化を検討した。具体的には、スルホン酸塩型高分子の合成と水系不斉反応、キラル第四級アンモニウム塩の合成と高分子固定化とそれを用いる不斉アルキル化反応を検討した。高分子不斉触媒を用いることかより、非常に高い光学純度の生成物を容易に得ることに成功し、高分子触媒は簡単に回収でき、再使用することができた。

  • Research Products

    (19 results)

All 2009 2008 Other

All Journal Article (6 results) (of which Peer Reviewed: 6 results) Presentation (10 results) Book (2 results) Remarks (1 results)

  • [Journal Article] Asymmetric Transfer Hydrogenation of Aromatic Ketones in Water using Polymer-supported Chiral Catalyst Containing Hy drophilic Pendant Group2009

    • Author(s)
      Arakawa, Y. ; Chiba, A. ; Haraguchi, N. ; Itsuno S
    • Journal Title

      Adv. Synth. Catal 350

      Pages: 2295-2304

    • Peer Reviewed
  • [Journal Article] Asymmetric transfer hydrogenation of imines catalyzed by pol ymer-immobilized chiral catalyst2009

    • Author(s)
      Haraguchi, N. ; Tsuru, K. ; Arakawa, Y. ; Itsuno, S
    • Journal Title

      Org. Biomol. Chem 7

      Pages: 69-75

    • Peer Reviewed
  • [Journal Article] Polymer-immobilized catalyst for asymmetric hydrogenation of racemic α-(N-benzoyl-N-methylamino)propiophenone2009

    • Author(s)
      Chiwara, V. I. ; Haraguchi, N. Itsuno, S
    • Journal Title

      J. Org. Chem. 74

      Pages: 1391-1393

    • Peer Reviewed
  • [Journal Article] Preparation of a Polymer-supported 1,2-Diamine and Its Appli cation to the Asymmetric Hydrogenation of Aromatic Ketones2008

    • Author(s)
      Takahashi, M. ; Haraguchi, N. ; Itsuno, S
    • Journal Title

      Tetrahedron Asymmetry 19

      Pages: 60-66

    • Peer Reviewed
  • [Journal Article] Effect of polymer Filling on Tensile Propaerties of Biomedic al Porous Pure Titanium2008

    • Author(s)
      Nakai, M. ; Niinomi, M. ; Akahori, T. ; Yamanoi, H. ; Itsuno, S. ; Haraguchi, N. ; Itoh, Y. ; Ogasawara, T. ; Onishi T
    • Journal Title

      J. Jpn. Soc. Powder Powder Metallurgy 55

      Pages: 312-317

    • Peer Reviewed
  • [Journal Article] Novel Immobilization Method of Chiral Quaternary Ammonium Salts onto Polymer2008

    • Author(s)
      Arakawa, Y. ; Haraguchi, N. ; Itsuno, S.
    • Journal Title

      Angew. Chem. Int. Ed. 43

      Pages: 8232-8235

    • Peer Reviewed
  • [Presentation] Polymer-immobilized chiral catalyst in aqueous media : Enviro nmentally benign synthetic method of optically active compounds (Plenary lecture)2009

    • Author(s)
      Itsuno, S
    • Organizer
      Bangladesh Chemical Congress
    • Place of Presentation
      Dhaka University, Ban gladesh
    • Year and Date
      20090130-0201
  • [Presentation] Synthesis and Characterization of Polymer-supported Chiral Catalyst and Its Application to Asymmetric Transfer Hydrogenation of Ketones and Imines2008

    • Author(s)
      Haraguchi, N. ; Arakawa, Y. ; Tsuru, K. ; Chiba, A. ; Itsuno, S
    • Organizer
      Japan-Korea Polymer Young Scientist Symposium
    • Place of Presentation
      Niigata, Japan
    • Year and Date
      20081022-25
  • [Presentation] Synthesis of Chiral Polycondensation Polymer and Its Application as a Reusable Chiral Catalyst to the Synthesis of a-Amino Acids2008

    • Author(s)
      Paul, D. K. ; Arakawa, Y. ; Haraguchi, N. ; Itsuno, S.
    • Organizer
      Polycondensation 2008
    • Place of Presentation
      Tokyo, Japan
    • Year and Date
      20080908-11
  • [Presentation] Asymmetric transfer hydrogenation of hydrophilic substrates with polymer-supported catalysts in water2008

    • Author(s)
      Chiba, A. ; Arakawa, Y. ; Ha raguchi, N. ; Itsuno, S
    • Organizer
      236th ACS National Meeting
    • Place of Presentation
      Philadelphia, PA, USA
    • Year and Date
      20080817-21
  • [Presentation] Preparation of polymer-supported chiral quaternary ammonium salt by novel immobilization method and its application to asymmetric alkylation2008

    • Author(s)
      Arakawa, Y. ; Haraguchi, N. ; Itsuno, S
    • Organizer
      236th ACS National Meeting
    • Place of Presentation
      Philadelphia, PA, USA
    • Year and Date
      20080817-21
  • [Presentation] Asymmetric transfer hydrogenation of imines with use of polymer-supported chiral catalyst2008

    • Author(s)
      Haraguchi, N. ; Tsuru, K. ; Itsuno, S
    • Organizer
      236th ACS National Meeting
    • Place of Presentation
      Philadelphia, PA, USA
    • Year and Date
      20080817-21
  • [Presentation] Asymmetric Reaction using Polymer-supported Chiral Quaternary Ammonium Salt2008

    • Author(s)
      Itsuno, S. ; Arakawa, Y. ; Paul, D. K. ; Haraguchi, N
    • Organizer
      20th International Symposium on Chirality (ISCD-20)
    • Place of Presentation
      Geneva, Switzerland
    • Year and Date
      20080706-09
  • [Presentation] Novel Synthetic Method of Polymer-Immobilized Chiral Catalysts and Their Use in Asymmetric Reactions2008

    • Author(s)
      Itsuno, S.
    • Organizer
      Organisch-chemisches Kolloquium at Basel University
    • Place of Presentation
      Basel, Switzerland
    • Year and Date
      2008-07-10
  • [Presentation] Asymmetric Hydrogenation via Dynamic Kinetic Resolution us ing Polymer-supported Catalyst2008

    • Author(s)
      Chiwara, V. I. ; Takahashi, M. ; Haraguchi, N. ; Itsuno, S
    • Organizer
      Third International Conference on Advance d Organic Synthesis Directed toward the Ultimate Efficiency and Practicability
    • Place of Presentation
      Ohtsu, Japan
    • Year and Date
      2008-05-26
  • [Presentation] symmetric Reaction with Polymer-Supported Chiral Organocatalyst prepared by Novel Immobilization Method2008

    • Author(s)
      Arakawa, Y. ; Haraguchi, N. Itsuno, S
    • Organizer
      Third International Conference on Advanced Organic Synthesis Directed toward the Ultimate Efficiency and Practicability
    • Place of Presentation
      Ohtsu, Japan
    • Year and Date
      2008-05-26
  • [Book] Heterogeneous Enantioselective Catalysis Using Organic Polymeric Supports2008

    • Author(s)
      Itsuno, S
    • Total Pages
      73-129
    • Publisher
      Wiley-VCH
  • [Book] Acid Catalysis in Modern Organic Synthesis2008

    • Author(s)
      Itsuno, S.
    • Total Pages
      1019-1060
    • Publisher
      Wiley-VCH
  • [Remarks]

    • URL

      http://www.tutms.tut.ac.jp/~haraguchi/sub9.html

URL: 

Published: 2010-06-11   Modified: 2016-04-21  

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