第四級アンモニウム塩型光学活性高分子の合成と不斉反応への応用

2008 Fiscal Year Annual Research Report

• Project/Area Number: 19550122
• Research Institution: Toyohashi University of Technology
• Principal Investigator: 伊津野 真一 Toyohashi University of Technology, 工学部, 教授 (50158755)
• Co-Investigator(Kenkyū-buntansha): 原口 直樹 豊橋技術科学大学, 工学部, 助教 (30378260)
• Keywords: 第四級アンモニウム塩 / ジアミン / ジハライド / キラル第四級アンモニウム塩 / シンコナアルカロイド / 光学活性高分子

Research Abstract

第三級アミンとハライドから第四級アンモニウム塩が生成する反応を利用して、ジアミンとジハライドとの反応で、第四級アンモニウム塩構造を繰り返し単位に有する高分子の合成法についての研究を行った。最初に構造解析などの容易なアキラルジアミンとジハライドを用いてこの重合法に関する基礎的知見を整理する必要があるため、アキラルなジアミンとして1,4-ジアザビシクロ[2.2.2]オクタン(DABCO)とジハライドにω-ジブロモキシレンの重合を検討して第四級アンモニウム塩高分子合成の詳細な条件検討を行った。種々反応条件を検討した結果、水、ジメチルホルムアミド混合溶媒中で、ジアミンとジハライドを加熱することにより、分子間で四級化反応が進行し、高分子を生成することがわかった。高分子主鎖に第四級アンモニウム塩構造を含むため得られた高分子の多くは、水溶性を示した。DABCOとジブロモキシレンとの重合では、メタおよびパラジブロモキシレンを用いた場合に高分子量の生成物が得られることを確認した。
次にキラル第四級アンモニウム塩構造を主鎖に含む光学活性高分子の合成についても検討を行った。第四級アンモニウム塩として、シンコナアルカロイド類を用いることにより、種々の光学活性第四級アンモニウム塩型高分子の合成に成功した。これらの光学活性高分子は、種々の有機反応の不斉触媒として作用することも明らかとなり、これまでにない、新規主鎖不斉型高分子触媒を開発することができた。

Research Products

• [Journal Article] Asymmetric transfer hydrogenation of imines catalyzed by polymer-immobilized chiral catalyst (2009)
  • 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) propiophenone (2009)
  • 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 Application to the Asymmetric Hydrogenation of Aromatic Ketones (2008)
  • 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 Biomedical Porous Pure Titanium (2008)
  • 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 Polymer (2008)
  • Author(s): Arakawa, Y., Haraguchi, N., Itsuno, S.
  • Journal Title: Angew. Chem. Int. Ed. 43 Pages: 8232-8235
  • Peer Reviewed
• [Journal Article] Asymmetric Transfer Hydrogenation of Aromatic Ketones in Water using Polymer-supported Chiral Catalyst Containing Hydrophilie Pendant Group (2008)
  • Author(s): Arakawa, Y., Chiba, A., Haraguchi, N., Itsuno S.
  • Journal Title: Adv. Synth. Catal. 350 Pages: 2295-2304
  • Peer Reviewed
• [Presentation] Polymer-immobilized chiral catalyst in aqueous media : Environmentally benign synthetic method of optically active compounds (Plenary lecture) (2009)
  • Author(s): Itsuno, S.
  • Organizer: Bangladesh Chemical Congress
  • Place of Presentation: Dhaka, Bangladesh
  • Year and Date: 20090130-20090201
• [Presentation] Synthesis and Characterization of Polymer-supported Chiral Catalyst and Its Application to Asymmetric Transfer Hydrogenation of Ketones and Imines (2008)
  • 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: 20081022-20081025
• [Presentation] Synthesis of Chiral Polycondensation Polymer and Its Application as a Reusable Chiral Catalyst to the Synthesis of α-Amino Acids (2008)
  • Author(s): Paul, D. K., Arakawa, Y., Haraguchi, N., Itsuno, S.
  • Organizer: Polycondensation 2008
  • Place of Presentation: Tokyo, Japan
  • Year and Date: 20080908-20080911
• [Presentation] Asymmetric transfer hydrogenation of hydrophilic substrates with polymer-supported catalysts in water (2008)
  • Author(s): Chiba, A., Arakawa, Y., Haraguchi, N., Isuno, S.
  • Organizer: 236th ACS National Meeting
  • Place of Presentation: Philadelphia, PA, USA
  • Year and Date: 20080817-20080821
• [Presentation] Preparation of polymer-supported chiral quaternary ammonium salt by novel immobilization method and its application to asymmetric alkylation (2008)
  • Author(s): Arakawa, Y., Haraguchi, N., Itsuno, S.
  • Organizer: 236th ACS National Meeting
  • Place of Presentation: Philadelphia, PA, USA
  • Year and Date: 20080817-20080821
• [Presentation] Asymmetric transfer hydrogenation of imines with use of polymer-supported chiral catalyst. (2008)
  • Author(s): Haraguchi, N., Tsuru, K., Itsuno, S.
  • Organizer: 236th ACS National Meeting
  • Place of Presentation: Philadelphia, PA, USA
  • Year and Date: 20080817-20080821
• [Presentation] Asymmetric Reaction using Polymer-supported Chiral Quaternary Ammonium Salt (2008)
  • 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: 20080706-20080709
• [Presentation] Novel Synthetic Method of Polymer-Immobilized Chiral Catalysts and Their Use in Asymmetric Reactions (2008)
  • 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 using Polymer-supported Catalyst (2008)
  • Author(s): Chiwara, V. I., Takahashi, M., 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
• [Presentation] symmetric Reaction with Polymer-Supported Chiral Organocatalyst prepared by Novel Immobilization Method (2008)
  • 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 Supports (2008)
  • Author(s): Itsuno, S.
  • Total Pages: 73-129
  • Publisher: Wiley-VCH
• [Book] Acid Catalysis in Modern Organic Synthesis (2008)
  • Author(s): Itsuno, S.
  • Total Pages: 1019-1060
  • Publisher: Wiley-VCH
• [Remarks]
  • URL: http://www.tutms.tut.ac.jp/~haraguchi/sub9.html