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両親媒性高分子不斉触媒の創製

Research Project

Project/Area Number 19020025
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionToyohashi University of Technology

Principal Investigator

伊津野 真一 (伊津野 慎一)  Toyohashi University of Technology, 工学部, 教授 (50158755)

Project Period (FY) 2007 – 2008
Project Status Completed (Fiscal Year 2008)
Budget Amount *help
¥4,400,000 (Direct Cost: ¥4,400,000)
Fiscal Year 2008: ¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 2007: ¥2,200,000 (Direct Cost: ¥2,200,000)
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 / 高分子固定化触媒 / 高分子固定化 / スルホン酸塩 / 水素移動型還元反応
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。

Report

(2 results)
  • 2008 Annual Research Report
  • 2007 Annual Research Report
  • Research Products

    (36 results)

All 2009 2008 2007 Other

All Journal Article (14 results) (of which Peer Reviewed: 14 results) Presentation (18 results) Book (3 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

    • Related Report
      2008 Annual Research Report
    • 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

    • Related Report
      2008 Annual Research Report
    • 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

    • Related Report
      2008 Annual Research Report
    • 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

    • Related Report
      2008 Annual Research Report
    • 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

    • Related Report
      2008 Annual Research Report
    • 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

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Preparation of a Polymer-supported 1,2-Diamine and Its Application to the Asymmetric Hydrogenation of Aromatic Ketones2008

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

      Tetrahedron Asymmetry 19

      Pages: 60-66

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Novel Polymers with Chiral 1,2-Diamine Moiety by Polycon densation and Their Application to Catalyst for Asymmetric Hydrogenation of Aromatic Ketones2007

    • Author(s)
      Haraguchi, N.; Prasad, N.; Uchiyama, T.; Itsuno, S.
    • Journal Title

      Macromol. Symp. 254

      Pages: 67-73

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Novel Preparation Method of Poly (L-lactide)-Based Block Coplymers: Extended Chain Crystallites as a Solid-State Macro-Coinitiator2007

    • Author(s)
      Tsuji, H.; Nishikawa, M.; Sakamoto, Y.; Itsuno, S.
    • Journal Title

      Biomacromolecules 8

      Pages: 1730-1738

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Melt-Processed Biodegradable Polyester Blends of Poly (L-lactic acid) and Poly (〓-caprolactone): Effects of Processing Conditions on Biodegradation2007

    • Author(s)
      Tsuji, H.; Horikawa, G.; Itsuno, S.
    • Journal Title

      J. Appl. Polym. Sci. 104

      Pages: 831-841

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Polymer-supported Chiral 1,2-Diamines by Radical Polymerization with Vinyl Monomer for Asymmetric Hydrogenation of Aromatic Ketones2007

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

      Macromol. Symp. 249-250

      Pages: 365-372

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Polymers Containing Chiral 1,2-Diamine Derivatives and Their Application to Asymmetric Reactions2007

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

      Pure and Appl. Chem. 79

      Pages: 448-454

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Hydrogenation of Aromatic Ketones using Polymeric Catalyst Prepared from Polymer-supported 1,2-Diamine2007

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

      J. Organomet. Chem. 692

      Pages: 487-494

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 高分子固定化型不斉触媒の進歩2007

    • Author(s)
      伊津野真一, 荒川幸弘, 原口直樹
    • Journal Title

      化学工業 58

      Pages: 269-274

    • Related Report
      2007 Annual Research Report
    • 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
    • Related Report
      2008 Annual Research Report
  • [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
    • Related Report
      2008 Annual Research Report
  • [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
    • Related Report
      2008 Annual Research Report
  • [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
    • Related Report
      2008 Annual Research Report
  • [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
    • Related Report
      2008 Annual Research Report
  • [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
    • Related Report
      2008 Annual Research Report
  • [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
    • Related Report
      2008 Annual Research Report
  • [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
    • Related Report
      2008 Annual Research Report
  • [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
    • Related Report
      2008 Annual Research Report
  • [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
    • Related Report
      2008 Annual Research Report
  • [Presentation] Polymer-Immobilized Chiral Catalyst for Asymmetric Reactions2007

    • Author(s)
      Itsuno, S.
    • Organizer
      International Symposium on Advanced Macromolecules and Nano-materials with Precisely Designed Architectures
    • Place of Presentation
      札幌
    • Year and Date
      2007-10-05
    • Related Report
      2007 Annual Research Report
  • [Presentation] Design and Synthesis of Novel Polymer-supported Chiral 1,2-Diamine for Asymmetric Hydrogenation2007

    • Author(s)
      Haraguchi, N.; Itsuno, S.
    • Organizer
      International Symposium on Advanced Macromolecules and Nano-materials with Precisely Designed Architectures
    • Place of Presentation
      札幌
    • Year and Date
      2007-10-05
    • Related Report
      2007 Annual Research Report
  • [Presentation] Polymer-Supported Chiral 1,2-Diamine Derivatives and Their Application to Asymmetric Reactions2007

    • Author(s)
      Itsuno, S.
    • Organizer
      3rd International Conference on Reactive Polymers in Inhomogeneous Systems, in Melts, and at Int erfaces
    • Place of Presentation
      Dresden, Germany
    • Year and Date
      2007-09-25
    • Related Report
      2007 Annual Research Report
  • [Presentation] 高分子固定化型光学活性第四級アンモニウム塩の合成と不斉反応への応用II2007

    • Author(s)
      荒川 幸弘, 原口 直樹, 伊津野 真一
    • Organizer
      高分子討論会
    • Place of Presentation
      名古屋
    • Year and Date
      2007-09-20
    • Related Report
      2007 Annual Research Report
  • [Presentation] Development of Novel Polymer-supported Chiral Ligand for Asymmetric Reactions2007

    • Author(s)
      Itsuno, S.
    • Organizer
      The 4th International Symposium on Advanced Materials in Asia-Pacific Rim
    • Place of Presentation
      新潟
    • Year and Date
      2007-07-14
    • Related Report
      2007 Annual Research Report
  • [Presentation] 高分子固定化型光学活性第四級アンモニウム塩の合成と不斉反応への応用2007

    • Author(s)
      荒川 幸弘, 原口 直樹, 伊津野 真一, 平尾 明, Macosko Christopher W.
    • Organizer
      高分子学会
    • Place of Presentation
      京都
    • Year and Date
      2007-05-30
    • Related Report
      2007 Annual Research Report
  • [Presentation] Synthesis of Polymer-Immobilized Chiral Diamine Derivatives and Their Application to Asymmetric Reactions in Water2007

    • Author(s)
      Itsuno, S.
    • Organizer
      2007 Korea-Japan Joint Forum on Living/Controlled Polymerization and the Related Subjects
    • Place of Presentation
      Gwangju, Korea
    • Year and Date
      2007-05-04
    • Related Report
      2007 Annual Research Report
  • [Presentation] 新規光学活性第四級アンモニウム塩の合成2007

    • Author(s)
      荒川幸弘、原口直樹、伊津野真一
    • Organizer
      日本化学会
    • Place of Presentation
      関西大学
    • Year and Date
      2007-03-27
    • Related Report
      2007 Annual Research Report
  • [Book] Heterogeneous Enantioselective Catalysis Using Organic Polymeric Supports2008

    • Author(s)
      Itsuno, S
    • Publisher
      Wiley-VCH
    • Related Report
      2008 Annual Research Report
  • [Book] Acid Catalysis in Modern Organic Synthesis2008

    • Author(s)
      Itsuno, S.
    • Publisher
      Wiley-VCH
    • Related Report
      2008 Annual Research Report
  • [Book] Acid Catalysis in Modern Organic Synthesis, Chapter 192008

    • Author(s)
      Itsuno, S.
    • Total Pages
      42
    • Publisher
      WILEY-VCH
    • Related Report
      2007 Annual Research Report
  • [Remarks]

    • URL

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

    • Related Report
      2008 Annual Research Report

URL: 

Published: 2007-04-01   Modified: 2018-03-28  

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