Synthesis of chiral quaternary ammonium polymers and their application to asymmetric reaction

• Project/Area Number: 19550122
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Polymer chemistry
• Research Institution: Toyohashi University of Technology
• Principal Investigator: ITSUNO Shinichi Toyohashi University of Technology, 工学部, 教授 (50158755)
• Co-Investigator(Kenkyū-buntansha): HARAGUCHI Naoki 豊橋技術科学大学, 工学部, 助教 (30378260)
• Project Period (FY): 2007 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000); Fiscal Year 2009: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000); Fiscal Year 2008: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2007: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
• Keywords: 光学活性高分子 / 第四級アンモニウム塩 / ジアミン / ジハライド / 高分子不斉触媒 / 不斉アルキル化反応 / キラル第四級アンモニウム塩 / シンコナアルカロイド / キラルジアミン / キラルジハライド / 四級化

Research Abstract

Although a substantial amount of work has been carried out using a side chain functionalized polymers, only a limited number of investigations have been performed to elucidate the use of main-chain functional polymers. The main-chain chiral polymer catalysts having rigid and sterically regular structure may have a better defined microenvironment at the catalytic sites and have allowed a systematic modification of their catalytic properties. We have synthesized two different types of chiral main-chain polymers containing quaternary ammonium salt structure. These chiral polymers were used as catalyst for asymmetric alkylation reaction of N-diphenylmethylidene glycine tert-butyl ester to give phenylalanine derivative in high level of enantioselectivity.

Research Products

• [Journal Article] Main-Chain Ionic Chiral Polymers: Synthesis of Optically Active Quaternary Ammonium Sulfonate Polymers and Their Application in Asymmetric Catalysis (2010)
  • Author(s): Shinichi Itsuno, Devproshad K. Paul, M.A. Salam, Naoki Haraguchi
  • Journal Title: J. Am. Chem. Soc. (in press)
  • Peer Reviewed
• [Journal Article] Main-Chain Ionic Chiral Polymers : Synthesis of Optically Active Quaternary Ammonium Sulfonate Polymers and Their Application in Asymmetric Catalysis (2010)
  • Author(s): Itsuno, S., Paul, D.K., Salam, M.A., Haraguchi, N.
  • Journal Title: J.Am.Chem.Soc. (In press)
  • Peer Reviewed
• [Journal Article] Novel Polymer-supported Organocatalyst via Ion Exchange Reaction : Facile immobilization of Chiral Imidazolidin-4-one and Its Application to Diels-Alder Reaction (2010)
  • Author(s): Haraguchi, N., Takemura, Yu, Itsuno, S.
  • Journal Title: Tetrahedron Lett. 51 Pages: 1205-1208
  • Peer Reviewed
• [Journal Article] Development of biomedical porous titanium filled with medical polymer by in-situ polymerization of monomer solution infiltrated into pores (2010)
  • Author(s): Masaaki Nakai, Mitsuo Niinomi, Toshikazu Akahori, Harumi Tsutsumi, Shinichi Itsuno, Naoki Haraguchi, Yoshinori Itoh, Tadashi Ogasawara, Takashi Onishi, Taku Shindoh
  • Journal Title: J.Mech.Behav.Biomed.Mater. 3 Pages: 41-50
  • Peer Reviewed
• [Journal Article] Immobilization Method of Chiral Catalysts onto Amphiphilic Polymer Supports (2009)
  • Author(s): Itsuno, S.
  • Journal Title: Syn.Org.Chem.Jpn. 67 Pages: 1025-1032
  • NAID: 10025644777
  • Peer Reviewed
• [Journal Article] Polymer-immobilized catalyst for asymmetric hydrogenation of racemic a-(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] 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] 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] Novel Immobilization Method of Chiral Quaternary Ammonium Salts onto Polymer (2008)
  • Author(s): Yukihiro Arakawa, Naoki Haraguchi, Shinichi Itsuno
  • Journal Title: Angew. Chem. Int. Ed. 43 Pages: 8232-8235
  • 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
• [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] Synthesis of Novel Polymers with Chiral 1, 2-Diamine Moiety by Polycon densation and Their Application to Catalyst for Asymmetric Hydrogenation of Aromatic Ketones (2007)
  • Author(s): Haraguchi, N.; Prasad, N.; Uchiyama, T.; Itsuno, S.
  • Journal Title: Macromol.Symp. 254 Pages: 67-73
  • Peer Reviewed
• [Journal Article] Novel Preparation Method of Poly(L-lactide)-Based Block Coplymers: Extended Chain Crystallites as a Solid-State Macro-Coinitiator (2007)
  • Author(s): Tsuji, H.; Nishikawa, M.; Sakamoto, Y.; Itsuno, S.
  • Journal Title: Biomacromolecules 8 Pages: 1730-1738
  • Peer Reviewed
• [Journal Article] Melt-Processed Biodegradable Polyester Blends of Poly(L-lactic acid) and Poly (-caprolactone): Effects of Processing Conditions on Biodegradation (2007)
  • Author(s): Tsuji, H.; Horikawa, G.; Itsuno, S.
  • Journal Title: J.Appl.Polym.Sci. 104 Pages: 831-841
  • Peer Reviewed
• [Journal Article] Polymer-supported Chiral 1, 2-Diamines by Radical Polymerization with Vinyl Monomer for Asymmetric Hydrogenation of Aromatic Ketones (2007)
  • Author(s): Haraguchi N.; Chiba, M.; Takahashi, M.; Itsuno, S.
  • Journal Title: Macromol.Symp. 249-250 Pages: 365-372
  • Peer Reviewed
• [Journal Article] Synthesis of Polymers Containing Chiral 1, 2-Diamine Derivatives and Their Application to Asymmetric Reactions (2007)
  • Author(s): Itsuno, S.; Takahashi, M.; Arakawa, Y.; Haraguchi, N.
  • Journal Title: Pure and Appl.Chem. 79 Pages: 448-454
  • Peer Reviewed
• [Journal Article] Asymmetric Hydrogenation of Aromatic Ketones using Polymeric Catalyst Prepared from Polymer-supported 1, 2-Diamine (2007)
  • Author(s): Itsuno, S.; Chiba, M.; Takahashi M.; Arakawa, Y.; Haraguchi, N
  • Journal Title: J.Organomet.Chem. 692 Pages: 487-494
  • 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
  • Peer Reviewed
• [Presentation] Immobilization Methods of Chiral Catalyst to Polymer and Asymmetric Reaction using Polymeric Catalyst (2009)
  • Author(s): 伊津野真一
  • Organizer: McMaster Chemistry lecture series
  • Place of Presentation: Ontario, Canada
  • Year and Date: 2009-07-10
• [Presentation] Synthesis of Polymers Containing Chiral Quaternary Ammonium Salt Structure and Their Application to Asymmetric Catalysts in Alkylation Reaction (2009)
  • Author(s): Shinichi Itsuno
  • Organizer: 2009 Taiwan-Japan Bilateral Polymer Symposium
  • Place of Presentation: Taipei, Taiwan
• [Presentation] Polymer-immobilized chiral catalyst in aqueous media: Enviromentally benign synthetic method of optically active compounds (Plenary lecture) (2009)
  • Author(s): Shinichi Itsuno
  • Organizer: Bangladesh Chemical Congress, Plenary lecture
  • Place of Presentation: Dhaka University, Bangladesh
• [Presentation] Synthesis of Main Chain Ionic Polymers via Quaternary Ammonium Sulfonate Formation Reaction (2009)
  • Author(s): 伊津野真一, 原口直樹
  • Organizer: 11th Pacific Polymer Conference PPC11
  • Place of Presentation: Cairns, Australia
• [Presentation] Medical Polymer Filling into Porous Titanium Fabricated by Powder Metallurgy and its Mechanical Functionality (2009)
  • Author(s): Mitsuo Niinomi, Masaaki Nakai, Toshikazu Akahori, Harumi Tsutsumi, Shinichi Itsuno, Naoki Haraguchi, Yoshinori Itoh, Tadashi Ogasawara, Takashi Onishi, Taku Shindoh
  • Organizer: Euro PM2009
  • Place of Presentation: Copenhagen, Danmark
• [Presentation] Preparation of Chiral Polymers Containing Quaternary Ammonium Sulfonate Structure and Their Use as Catalyst for Asymmetric Reactions (2009)
  • Author(s): 伊津野真一
  • Organizer: 13th International IUPAC Conference on Polymers and Organic Chemistry (POC 09)
  • Place of Presentation: Montreal, Canada
• [Presentation] 新規スルホン酸塩型高分子固定化不斉有機分子触媒の開発 (2009)
  • Author(s): 辻村麻美, 原口直樹, 伊津野真一
  • Organizer: 第40回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 岐阜大学
• [Presentation] 高分子固定化型触媒を用いた環状スルホンイミンの水素移動型不斉還元反応 (2009)
  • Author(s): 杉江治城, 原口直樹, 伊津野真一
  • Organizer: 第40回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 岐阜大学
• [Presentation] 高分子固定化型シンコニジン第四級アンモニウ塩ダイマーの新規開発と不斉アルキル化反応への応用 (2009)
  • Author(s): 内藤航, 原口直樹, 伊津野真一
  • Organizer: 第40回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 岐阜大学
• [Presentation] 第四級アンモニウム塩型高分子固定化キラル触媒を用いた水系での水素移動型不斉還元反応 (2009)
  • Author(s): 落合孝佳, 原口直樹, 伊津野真一
  • Organizer: 第40回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 岐阜大学
• [Presentation] 高分子固定化 MacMillan 触媒の新規開発と不斉反応への応用 (2009)
  • Author(s): 金子昌広, 竹村由, 原口直樹, 伊津野真一
  • Organizer: 第40回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 岐阜大学
• [Presentation] 酒石酸誘導体第4級アンモニウム塩の高分子固定化とグリシン誘導体の不斉アルキル化触媒への応用 (2009)
  • Author(s): 大石あず沙, 原口直樹, 伊津野真一
  • Organizer: 第40回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 岐阜大学
• [Presentation] 新規高分子固定化型不斉キラルジアミンの合成と不斉反応への応用II (2009)
  • Author(s): 原田旭大, 原口直樹, 伊津野真一
  • Organizer: 第40回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 岐阜大学
• [Presentation] Synthesis of cinchona derived sulfonated polymers and their application to the asymmetric reactions (2009)
  • Author(s): Parvez Md.Masud, 原口直樹, 伊津野真一
  • Organizer: 第40回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 岐阜大学
• [Presentation] タンパク質のアミノ酸配列におけるシスペプチド構造に関する統計的解析 (2009)
  • Author(s): 全炳宇, 伊津野泰子, 原口直樹, 伊津野真一
  • Organizer: 第40回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 岐阜大学
• [Presentation] イオン結合による MacMillan 触媒の新規高分子固定化と不斉 Diels-Alder 反応への応用 (2009)
  • Author(s): 竹村由, 原口直樹, 伊津野真一
  • Organizer: 第58回高分子討論会
  • Place of Presentation: 熊本大学
• [Presentation] 高分子固定化型不斉触媒によるイミンの水素移動型不斉還元反応VI (2009)
  • Author(s): 原口直樹, 都留慶一, 伊津野真一
  • Organizer: 第58回高分子討論会
  • Place of Presentation: 熊本大学
• [Presentation] キラルリガンドを結合した高分子微粒子の合成と不斉反応への応用 (2009)
  • Author(s): 西山晃洋, 原口直樹, 伊津野真一
  • Organizer: 第58回高分子討論会
  • Place of Presentation: 熊本大学
• [Presentation] タンパク質を持つアミノ酸配列におけるシスペプチド構造に関する統計的解析 (2009)
  • Author(s): 全炳宇, 伊津野泰子, 原口直樹, 伊津野真一
  • Organizer: 日本化学会第89春季大会
  • Place of Presentation: 日本大学
• [Presentation] カチオン型高分子固定化型不斉触媒を用いたa-ケト酸誘導体の水系での不斉水素移動反応 (2009)
  • Author(s): 千葉温子, 荒川幸弘, 原口直樹, 伊津野真一
  • Organizer: 日本化学会第89春季大会
  • Place of Presentation: 日本大学
• [Presentation] Polymer-supported Catalysts for Asymmetric Hydrogenation via Dynamic Kinetic Resolution (2009)
  • Author(s): Naoki Haraguchi, Vinia Ipai Chiwara, Shinichi Itsuno
  • Organizer: 日本化学会第89春季大会
  • Place of Presentation: 日本大学
• [Presentation] キラル第四級アンモニウム塩触媒の新規高分子固定化法と不斉反応への応用 (2009)
  • Author(s): 伊津野真一, 荒川幸弘, 大石あず沙, 原口直樹
  • Organizer: 日本化学会第89春季大会
  • Place of Presentation: 日本大学
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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
• [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II (2007)
  • 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
• [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
• [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
• [Book] "使える!有機合成反応実践のてびき" "高分子固定化触媒による水素移動型不斉還元反応" "高分子固定化不斉触媒によるグリシン誘導体の不斉アルキル化反応" "高分子固定化不斉触媒による動的速度論的分割を伴う不斉水素化反応" (2010)
  • Author(s): 伊津野真一
  • Publisher: 化学同人
• [Book] 使える!有機合成反応 実践のてびき (2010)
  • Author(s): 伊津野真一
  • Total Pages: 6
  • Publisher: 化学同人
• [Book] "Heterogeneous Enantioselective Catalysis Using Organic Polymeric Suopports" In Handbook of Asymmetric Heterogeneous Catalysis, Chapter 3 (Ding, K. ; Uozumi, Y. Eds. : Wiley-VCH, Weinheim) (2008)
  • Author(s): Shinichi Itsuno, Naoki Haraguchi
• [Book] Handbook of Asymmetric Heterogeneous Catalysis (2008)
  • Author(s): Shinichi Itsuno, Naoki Haraguchi
  • Total Pages: 56
  • Publisher: Wiley-VCH
• [Book] Acid Catalysis in Modern Organic Synthesis (2008)
  • Author(s): 伊津野真一
  • Total Pages: 56
  • Publisher: Wiley-VCH
• [Book] Heterogeneous Enantioselective Catalysis Using Organic Polymeric Supports (2008)
  • Author(s): Itsuno, S.
  • Publisher: Wiley-VCH
• [Book] Acid Catalysis in Modern Organic Synthesis (2008)
  • Author(s): Itsuno, S.
  • Publisher: Wiley-VCH
• [Book] Acid Catalysis in Modern Organic Synthesis, Chapter 19 (2008)
  • Author(s): Itsuno, S.
  • Total Pages: 42
  • Publisher: WILEY-VCH
• [Remarks]
  • URL: http://www.tutms.tut.ac.jp/~haraguchi/sub9.html
• [Remarks]
  • URL: http://www.tutms.tut.ac.jp/~haraguchi/sub9.html
• [Remarks]
  • URL: http://www.tutms.tut.ac.jp/~haraguchi/sub9.html
• [Patent(Industrial Property Rights)] 光学活性4級アンモニウム担持ポリマーとその製造方法ならびに光学活性アミノ酸類の製造方法 (2009)
  • Inventor(s): 伊津野真一, 久保田靖, 井上勉
  • Industrial Property Rights Holder: 豊橋技術科学大学、日本曹達株式会社
  • Patent Publication Number: 2009-235393
  • Filing Date: 2009-02-27
• [Patent(Industrial Property Rights)] 特許 (2009)
  • Inventor(s): 伊津野真一, 久保田靖, 井上勉
  • Industrial Property Rights Holder: 豊橋技術科学大学, 日本曹達株式会社
  • Patent Publication Number: 2009-235393
  • Filing Date: 2009-02-27