The Synthesis of enantiomerically pure novel liquid crystal compounds containing the bis(trifluoromethyl)alkanediol moiety.

• Project/Area Number: 16550125
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Functional materials chemistry
• Research Institution: Kagawa University
• Principal Investigator: TAKAGI Yumiko Kagawa University, Faculty of Education, Assistant Professor, 教育学部, 助教授 (50263413)
• Co-Investigator(Kenkyū-buntansha): NISHIHARA Hiroshi Kagawa University, Faculty of Education, Professor, 教育学部, 教授 (80036029) ; ITOH Toshiyuki Tottori University, Faculty of Engineering, Professor, 工学部, 教授 (50193503)
• Project Period (FY): 2004 – 2006
• Project Status: Completed (Fiscal Year 2006)
• Budget Amount: ¥3,700,000 (Direct Cost: ¥3,700,000); Fiscal Year 2006: ¥700,000 (Direct Cost: ¥700,000); Fiscal Year 2005: ¥700,000 (Direct Cost: ¥700,000); Fiscal Year 2004: ¥2,300,000 (Direct Cost: ¥2,300,000)
• Keywords: Ferroelectric liquid crystal compounds / Anti-ferroelectric liquid crystal compounds / Lipase / Fluoro Alkanol / Optically Pure

Research Abstract

Ant ferroelectric liquid crystal compounds(AFCLs), which possess a chiral 1,1,1-trifluoromethyl-2-alkanol moiety, are known to be important high-speed switching devices. Kusumoto and his colleagues recently the synthesis of unique dimeric AFLCs molecules which contain optically active bis(trifluoromethyl)alkanediols as chiral core units. The reported means for preparing optically pure bis(trifluoromethyl)alkanediols, however, required a nuisance resolution process using HPLC on chiral phase. We previously reported that Candida antarctica lipase catalyzed trans-esterification of racemic 1,1,1-trifluoro-2-alkanols with perfect enantioselectivity. We also achieved the hydrolysis of acetate more effectively. We next attempted trans-sterification of diol 1 in organic solvent using vinyl acetate as an acyl donor. Trans-esterification, however, did not take place. Fortunately, hydrolysis reaction of (±)-1 proceeded smoothly to provide monoacetate and diol with efficient enantioselectivity. We report the results of lipase-catalyzed hydrolysis reaction of bis(trifluoromethyl)alkanediols. Using optically active bis(trifluormethyl)-alkanediols obtained in this reaction as starting materials, synthesis of novel dimer type AFCLs has been demonstrated.

Research Products

• [Journal Article] Alkylation of N-protecting group free indole with vinyl ketones using iron salt catalyst (2007)
  • Author(s): Itoh, T., Uehara, H., Ogiso, K., Nomura, S., Hayase, S., Kawatsura, M.
  • Journal Title: Chemistry Letters 36・1 Pages: 50-51
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Ruthenium-catalysed linear-selective allylic alkylation of allyl acetates (2007)
  • Author(s): Kawatsura, M., Ata, F., Wada, S., Hayase, S., Uno, H., Itoh, T.
  • Journal Title: Chemical Communications Pages: 298-300
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Gem-Difluorocyclopropane as Core Molecule Candidate for Liquid Crystal Compounds (2007)
  • Author(s): Itoh, T., Kanbara, M., Ohashi, M., Hayase, S., Kawatsura, M., Kato T., Miyazawa, K., Takagi, Y., Uno, H.
  • Journal Title: J. Fluorine. Chem (inpress)
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] イオン液体中の酵素反応 (2007)
  • Author(s): 伊藤敏幸
  • Journal Title: 現代化学 No432・3 Pages: 28-32
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Alkylation of N-Protecting Group-free Indole with Vinyl Ketones Using Iron Salt Catalyst (2007)
  • Author(s): Itoh, T., Uehara, H., Ogiso, K., Nomura, S., Hayase, S., Kawatsura, M
  • Journal Title: Chem. Lett 36 Pages: 50-51
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Ruthenium-catalysed linear-selective allylic allylation of allyl acetates (2007)
  • Author(s): Kawatsura, M., Ata, F., Wada, S., Hayase, S., Uno, H., Itoh, T.
  • Journal Title: Chemical Communications Pages: 298-300
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Gem-Difluorocyclopropane as Core Molecule Candidate for Liquid Crystal Compounds (2007)
  • Author(s): Itoh, T., Kanbara, M., Ohashi, M., Hayase, S., Kawatsura, M., Kato, T., Miyazawa, K., Takagi, Y., Uno, H.
  • Journal Title: J.Fluorine.Chem (inpress)
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Enzymatic reaction using Ionic Liquid. (2007)
  • Author(s): Itoh Toshiyuki
  • Journal Title: Modern chemistry 432(3) Pages: 28-32
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Alkylation of N-protecting Group-free Indole with Vinyl Ketones using Iron Salt Catalyst (2007)
  • Author(s): Itoh, T;, Uehara, H;, Ogiso, K;, Nomura, S;, Hayase, S;, Kawatsura, M
  • Journal Title: Chem.Lett 36 Pages: 50-51
• [Journal Article] Biotransformation in ionic liquid (2007)
  • Author(s): Toshiyuki Itoh
  • Journal Title: Future Directions in Biocatalysis ( Ed. T.Matsuda a Elsevier Bioscience The Netherlands) (In press)
• [Journal Article] Gem-Difluorocyclopropane as Core Molecule Candidate for Liquid Crystal Compounds, (2007)
  • Author(s): Itoh, T;, Kanbara, M;, Ohashi, M;, Hayase, S;, Kawatsura, M;, Kato, T;, Miyazawa, K;, Takagi, Y;, Uno, H.
  • Journal Title: J.Fluorine.Chem (In press)
• [Journal Article] Preparation of Novel Hydrophobic Fluorine-substituted-alkyl sulfate Ionic Liquids and Application as an Efficient Reaction Medium for Lipase-catalyzed Reaction (2006)
  • Author(s): Tsukada, Yasuhiro, Iwamoto, Kazuhisa, Furutani, Hiroyuki, Matsushita, Yuichi, Abe, Yoshikazu, Matsumoto, Kei, Monda, Keishi, Hayase, Shuichi, Kawatsura, Motoi, Itoh, Toshiyuki
  • Journal Title: Tetrahedron Letters 48 Pages: 1801-1804
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] A novel 1,4-addition type reaction of β-keto esters with vinyl ketones catalyzed by iron(II)tetrafluoroborate in an ionic liquid solvent system (2006)
  • Author(s): Uehara, H., Nomura, S., Hayase, S., Kawatsura, M., Itoh, T.
  • Journal Title: Electrochemistry 74・8 Pages: 635-638
  • NAID: 10017390086
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Synthesis of novel gem-difluorinatedcyclopropane hybrids : applications for DNA cleavage agents switched by photo irradiation (2006)
  • Author(s): Ninomiya, Keiko, Tanimoto, Kunihiko, Ishida, Nanae, Horiii, Daisuke, Sisido Masahiko, Itoh, Toshiyuki
  • Journal Title: J. Fluorine Chem Pages: 651-656
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Palladium-catalyzed regioselective allylic alkylation of 1-aryl-2,3,3-trifluoroallyl acetates (2006)
  • Author(s): Kawatsura, M., Wada, S., Hayase, S., Itoh, T.
  • Journal Title: SYNLETT Pages: 2483-2485
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Enhanced enantioselectivity and remarkable acceleration of lipase-aatalyzed transesterification using an Imizadolium PEG-alkyl sulfate ionic liquid (2006)
  • Author(s): Itoh, T., Matsushita, Y, Abe, Y., Han, S-H., Wada, S., Hayase, S., Kawatsura, M., Takai, S., Morimoto, M., Hirose, Y.
  • Journal Title: Chemistry-A European Journal 12 Pages: 9228-9237
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] A novel 1,4-addition type reaction of b-keto esters with vinyl ketones catalyzed by iron(II)tetrafluoroborate in an ionic liquid solvent system (2006)
  • Author(s): Uehara, H., Nomura, S., Hayase, S., Kawatsura, M., Itoh, T
  • Journal Title: Electrochemistry 74 Pages: 635-638
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Synthesis of novel gem-difluorinatedcyclopropane hybrids : applications for DNA cleavage agents switched by photo irradiation (2006)
  • Author(s): Ninomiya, Keiko, Tanimoto, Kunihiko, Ishida, Nanae, Horiii, Daisuke, Sisido Masahiko, Itoh, Toshiyuki
  • Journal Title: J.Fluorine Chem 127 Pages: 651-656
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Enhanced enantioselectivity and remarkable acceleration of lipase-aatalyzed transesterification using an Imizadolium PEG-alkyl sulfate ionic liquid (2006)
  • Author(s): Kawatsura, M., Wada, S., Hayase, S., Itoh, T
  • Journal Title: Synlett. Pages: 2483-2485
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] A Novel 1,4-Addition Type Reaction of β-Keto Esters with Vinyl Ketones Catalyzed by Iron(II)tetrafluoroborate in an Ionic Liquid Solvent System (2006)
  • Author(s): Itoh, T., Matsushita, Y., Abe, Y., Han, S-H., Wada, S., Hayase, S., Kawatsura, M., Takai, S., Morimoto, M., Hirose, Y.
  • Journal Title: Chemistry-A European Journal 12 Pages: 9228-9237
  • NAID: 10017390086
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] A Novel 1,4-Addition Type Reaction of b-Keto Esters with Vinyl Ketones Catalyzed by Iron (II) tetrafluoroborate in an Ionic Liquid Solvent System (2006)
  • Author(s): Uehara, Hiroyuki, Nomura, Shun, Hayase, Shuichi, Kawatsura, Motoi, Itoh, Toshiyuki
  • Journal Title: Electrochemistry (in press)
• [Journal Article] Synthesis of novel gem-difluorinatedcyclopropane hybrids: applications for DNA cleavage agents switched by photo irradiation (2006)
  • Author(s): Ninomiya, Keiko, Tanimoto, Kunihiko, Ishida, Nanae, Horiii, Daisuke, Sisido Masahiko, Itoh, Toshiyuki
  • Journal Title: J Fluorine Chem 127(in press)
• [Journal Article] Novel alkylation of indole and pyrrole derivatives using Iron (II) tetrafluoroborate as a catalyst in an ionic liquid solvent (2006)
  • Author(s): Itoh, Toshiyuki
  • Journal Title: Abstracts of Papers, 231st ACS National Meeting, Atlanta, GA, Unit ed States, March 26-30, 2006
• [Journal Article] Enhanced enantioselectivity and stabilization of an enzyme using novel ionic liquids (2005)
  • Author(s): Itoh, T., Han, S., Matsushita, Y., Wada, S., Hayase, S., Hayase, S., Ohara, H., Oyama, M.
  • Journal Title: Separation and Purification Technology 41(In press)
• [Journal Article] Synthesis of novel liquid crystal compounds which have bis(trifluoromethyl)alkanediol moiety in optically pure form (2004)
  • Author(s): Takagi, Y., Yamana, F., Sumino, F., Ito, H., Yoshida, T., Kato, T., Miyazawa, K., Itoh, T.
  • Journal Title: Tetrahedron; Asymmetry 15 Pages: 2591-2594
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Synthesis of Optically Active gem-Difluorocyclopropanes through a Chemo-Enzymatic Reaction Strategy (2004)
  • Author(s): Itoh, T., Ishida, N., Mitsukura, K., Hayase, S., Ohashi, K.
  • Journal Title: J. Fluorine Chem 125 Pages: 775-783
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Enhanced Enantioselectivity and Remarkable Acceleration on the Lipase-Catalyzed Transeste rification Using Novel Ionic Liquids (2004)
  • Author(s): Itoh, T., Han, S., Matsushita, Y., Hayase, S.
  • Journal Title: Green Chemistry 6・9 Pages: 437-439
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] ヘッドライン 注目される新しい化学反応場,反応媒体"テーラメイドなイオン性液体を反応媒体とする酵素反応" (2004)
  • Author(s): 伊藤敏幸
  • Journal Title: 化学と教育 52・8 Pages: 520-523
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] イオン性液体中の酵素反応 (2004)
  • Author(s): 伊藤敏幸
  • Journal Title: 機能材料 24・11 Pages: 27-33
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] The Synthesis of enantiomerically pure novel liquid crystal compounds containing the bis(trifluoromethyl)alkanediol moiety. (2004)
  • Author(s): Takagi, Y, Yamana, F., Sumino, F., Ito, H., Yoshida, T., Kato, T., Miyazawa, K., Itoh, T.
  • Journal Title: Tetrahedron ; Asymmetry 15 Pages: 2591-2594
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Synthesis of Optically Active gem-Difluorocyclopropanes through a Chemo-Enzymatic Reaction Strategy (2004)
  • Author(s): Itoh, T., Ishida, N., Mitsukura, K., Hayase, S., Ohashi, K.
  • Journal Title: J.Fluorine Chem 125 Pages: 775-783
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Hayase, Enhanced Enantioselectivity and Remarkable Acceleration on the Lipase-Catalyzed Transesterification Using Novel Ionic Liquids (2004)
  • Author(s): Itoh, T., Han, S., Matsushita, Y.
  • Journal Title: Green Chemistry 6-9 Pages: 437-439
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Enzymatic Reaction using Ionic Liquids as a tailor-made solvent. (2004)
  • Author(s): Itoh, T.
  • Journal Title: Chemical Fducation Japan 52 Pages: 520-528
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Enzymatic Reaction using Ionic Liquids (2004)
  • Author(s): Itoh, T.
  • Journal Title: Functional materials 24 Pages: 24-33
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Synthesis of novel liquid crystal compounds which have bis(trifluoromethyl)alkanediol moiety in optically pure form (2004)
  • Author(s): Takagi, Y., Yamaha, F., Sumino, F., Ito, H., Yoshida, T., Kato, T., Miyazawa, K., Itoh, T.
  • Journal Title: Tetrahedron ; Asymmetry 15 Pages: 2591-2594
• [Journal Article] Enhanced Enantioselectivity and Remarkable Acceleration on the Lipase-Catalyzed Transesterification Using Novel Ionic Liquids (2004)
  • Author(s): Itoh, T., Han, S., Matsushita, Y., Hayase, S.
  • Journal Title: Green Chemistry 6・9 Pages: 437-439
• [Journal Article] A Novel 1,4-Addition Type Reaction of b-Keto Esters with vinyl Ketones Catalyzed by Iron(II)tetrafluoroborate in an Ionic Liquid Solvent System
  • Author(s): Uehara, Hiroyuki;, Nomura, Shun;, Hayase, Shuichi;, Kawatsura, Motoi;, Itoh, Toshiyuki
  • Journal Title: Electrochemistry 7 Pages: 635-638
• [Book] イオン液体と触媒 (2007)
  • Author(s): 伊藤敏幸
  • Publisher: 触媒(In press)
• [Book] イオン液体中の酵素反応 (2007)
  • Author(s): 伊藤敏幸
  • Publisher: 現代化学(In press)
• [Book] イオン液体を反応媒体に用いる酵素触媒反応 酵素開発・利用の最新技術,第4編第1章(監修 : 今中忠行) (2006)
  • Author(s): 伊藤敏幸
  • Total Pages: 309
  • Publisher: CMC出版
  • Description: 「研究成果報告書概要(和文)」より
• [Book] イオン液体II-驚異的な進歩と多彩な近未来-「イオン液体を反応媒体に用いるリパーゼ触媒反応」(大野弘幸編) (2006)
  • Author(s): 伊藤敏幸
  • Total Pages: 299
  • Publisher: CMC出版
  • Description: 「研究成果報告書概要(和文)」より
• [Book] 「イオン液体を反応媒体に用いる酵素触媒反応」酵素開発・利用の最新技術酵素 開発・利用の最新技術(監修:今中忠行)4編1章 (2006)
  • Author(s): 伊藤敏幸
  • Publisher: CMC出版
• [Book] イオン液体II-驚異的な進歩と多彩な近未来-,大野弘幸編,東京 (2006)
  • Author(s): 伊藤敏幸
  • Publisher: CMC出版
• [Book] Optically Active gem-Difluorocyclopropanes; Synthesis and Application for Novel Molecular Materials, ACS Symposium Series #911 (2005)
  • Author(s): Itoh, T.
  • Publisher: Oxford University Press/ American Chemical Society : Washington DC
  • Description: 「研究成果報告書概要(和文)」より
• [Book] "Fluorine-Containing Synthons," ACS Symposium Series #911, Ed, V. A. Soloshonok (2005)
  • Author(s): Itoh, Toshiyuki
  • Publisher: Oxford University Press/ American Chemical Society: Washington DC
• [Book] Optically_Active gem-Difluorocyclopropanes, Synthesis and Application for Novel Molecular Materials, ACS Symposium Series #911 (2005)
  • Author(s): Itoh, T.
  • Publisher: Oxford University Press/ American Chemical Society : Washington DC
• [Book] Analytical Mechanistic and Synthetic Organic Electrochemistry-6th International M. Baizer Award Symposium in Honor of Dennis H. Evans and Masao Tokuda (2004)
  • Author(s): Itoh, T., Uehara, H., Kawai, K., Hayase, S., Ohara, H., Oyama, M.
  • Publisher: The Electrochemical Society, Inc. USA
  • Description: 「研究成果報告書概要(和文)」より
• [Book] Analytical Mechanistic and Synthetic Organic Electrochemistry- 6th International M.Baizer Award Symposium in Honor of Dennis H.Evans and Masao Tokuda (2004)
  • Author(s): Itoh, T., Uehara, H., Kawai, K., Hayase, S., Ohara, H., Oyama, M.
  • Publisher: The Electrochemical Society, Inc.USA
• [Patent(Industrial Property Rights)] ポイントジフルオロ化イオン液体 (2006)
  • Inventor(s): 伊藤敏幸, 古谷浩行, 塚田泰弘
  • Industrial Property Rights Holder: 鳥取大学
  • Industrial Property Number: 2006-014677
  • Filing Date: 2006-01-25
  • Description: 「研究成果報告書概要(和文)」より
• [Patent(Industrial Property Rights)] 磁性を有するフラーレン誘導体 (2006)
  • Inventor(s): 伊藤敏幸, 古谷浩行
  • Industrial Property Rights Holder: 鳥取大学, 株式会社カネカ
  • Industrial Property Number: 2006-119762
  • Filing Date: 2006-04-24
  • Description: 「研究成果報告書概要(和文)」より
• [Patent(Industrial Property Rights)] 磁性を有するフラーレン誘導体 (2006)
  • Inventor(s): 伊藤敏幸, 古谷浩行
  • Industrial Property Rights Holder: 鳥取大学長 能勢隆之
  • Filing Date: 2006-04-24