• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Highly sensitive enantiomeric discrimination of chiral branched alkyl chains of fatty alcohols and amines, and the application to determine absolute stereochemistry of natural occurring products

Research Project

Project/Area Number 16380076
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Bioproduction chemistry/Bioorganic chemistry
Research InstitutionTohoku University

Principal Investigator

AKASAKA Kazuaki  Tohoku University, Graduate School of Life Sciences, Associate Professor, 大学院生命科学研究科, 助教授 (10201881)

Co-Investigator(Kenkyū-buntansha) 大類 洋  東北大学, 大学院・生命科学研究科, 教授 (20100050)
清水 弘樹  独立行政法人, 産業技術総合研究所・北海道センター, 研究員 (30344716)
Project Period (FY) 2004 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥9,900,000 (Direct Cost: ¥9,900,000)
Fiscal Year 2006: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 2005: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2004: ¥6,400,000 (Direct Cost: ¥6,400,000)
KeywordsChiral alcohols / Chiral amines / Enantiomeric discrimination / High performance liquid chromatography / Fluorescence derivatization / Insect pheromones / Nuclear magnetic resonance / Stereochemistry / 蛍光誘導体化法 / 光学活性化合物 / 分岐アルキル / キラル誘導体化試薬 / 蛍光誘導体化試薬 / 分岐アルコール
Research Abstract

(1R,2R)-and (1S,2S)-2-(2,3-Anthracenedicarboximide)cyclohexane carboxylic acids were developed as chiral fluorescent derivatization reagents. The reagents made it possible to discriminate the chirality of branched alkyl chain of primary and secondary alcohols having a chiral methyl branch remote from the hydroxyl group with at least 8 methylene spacers. Especially the HPLC method made it possible to discriminate their chirality with 10^<-15> mole levels by fluorometric detection. The reagents also made it possible to discriminate chirality of secondary alcohols by both the ^1H-NMR and the reversed-phase HPLC. Since chiral secondary alcohols having a methyl branched alkyl chain were separated into more than 3 peaks by the reversed-phase HPLC, it was possible to discriminate the chirality of the hydroxyl group and the alkyl branch simultaneously. Similarly, it was possible to discriminate chirality of amines having a chiral branched alkyl chain by using the acid chloride of the reagents. … More The combination of derivatization method using these reagents and 2D-HPLC were successfully applied to determine the absolute configurations and stereoisomers constitution of insect pheromones of the screw warm fly, Cochliomyia hominivorax, and the cowpea weevil, Callosobruchus maculate, respectively. Moreover, doubly checking method by using both enantiomers of the reagents was very useful to confirm the results.
We also synthesized new chiral fluorescence labeling reagents having a 2,3-anthracenedicarboximide group from D-glucosamine, and it was possible to introduce target alcohols at the anomeric positions of the reagents with β-selectivity by glycosidations. Especially, it was possible to use methyl glycoside reagent as a glycosyl donor with a Lewis acid and microwave irradiation, and it gave selectively β-glycoside while the reaction without microwave irradiation gave α-and β-mixed glycosides. Those reagents showed very high chiral discrimination ability, and they made it possible to separate the eight stereoisomers of 4,8,12,16-tetramethylheptadecanol and a-tocopherol by HPLC after derivatizations. Less

Report

(4 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (22 results)

All 2007 2006 2005

All Journal Article (22 results)

  • [Journal Article] Selectivity Enhancement for trans-2-(2,3-Anthracene-dicarboximido)cyclohexane-Derived Diastereomers in HPLC by using an Ordered Organic Stationary phase2007

    • Author(s)
      Atsushi Shundo, Kazuaki Akasaka, 他5名
    • Journal Title

      Analytical Sciences 23

      Pages: 311-315

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Selectivity Enhancement for trans-2-(2,3- Anthracendicarboximido)cyclohexane Derived Diastereomers in HPLC by using an Ordered Organic Stationary phase2007

    • Author(s)
      Atsushi Shundo, Megumi Fukui, Makoto Takafuji, Kazuaki Akasaka, Hiroshi Ohrui, Dusan Berek, Hirotaka Ihara
    • Journal Title

      Analytical Sciences 23

      Pages: 311-315

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Selectivity Enhancement for trans-2-(2,3-Anthracendicarbox-imido)cyclohexane-Derived Diastereomers in HPLC by using an Ordered Organic Stationary phase2007

    • Author(s)
      Atsushi Shundo, Kaguaki Akasaka, 他5名
    • Journal Title

      Analytical Sciences 23

      Pages: 311-315

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Direct determination of the stereoisomers constitution by 2D-HPLC and stereochemistry -pheromone acitivity relationship of the copulation release pheromone of the cowpea weevil, Callosobruchus maculate2006

    • Author(s)
      Tomonori Nakai, Arata Yajima, Kazuaki Akasaka, 他5名
    • Journal Title

      Tetrahedron 62

      Pages: 4590-4596

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] Chiral Discrimination of Primary Amins by HPLC After Labeling with a Chiral Derivatization Reagent, trans-2-(2,3-Anthracenedicarbox- imido)cyclohexanecarbonyl Chloride2006

    • Author(s)
      Kazuaki Akasaka, Takashi Ohtaki, Hiroshi Ohrui
    • Journal Title

      Journal of Separation Science 29

      Pages: 1390-1398

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Absolute Stereochemistry of Fungal Beauveriolide III and ACAT Inhibitory Activity of Four Stereoisomers2006

    • Author(s)
      Ohshiro, T., Akasaka, K.他8名
    • Journal Title

      Journal of Organic Chemistry 71

      Pages: 7643-7649

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Direct determination of the stereoisomers constitution by 2D-HPLC and stereochemistry-pheromone acitivity relationship of the copulation release pheromone of the cowpea weevil, Callosobruchus maculates2006

    • Author(s)
      Arata Yajima, Kazuaki Akasaka, Tomonori Bakai, Hiroki Maehara, Tomoo Nukada, Hiroshi Ohrui, Goro Yabuta
    • Journal Title

      Tetrahedron 62

      Pages: 4590-4596

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Chiral Discrimination of Primary Amins by HPLC After Labeling with a Chiral Derivatization Reagent, trans-2-(2,3-Anthracenedicarboximido)cyclohexanecarbonyl Chloride2006

    • Author(s)
      Kazuaki Akasaka, Takashi Ohtaki, Hiroshi Ohrui
    • Journal Title

      J.Separation Science 29(10)

      Pages: 1390-1398

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Absolute Stereochemistry of Fungal Beauveriolide III and ACAT Inhibitory Activity of Four Stereoisomers2006

    • Author(s)
      Ohshiro, T., Namatame, I., Nagai, K., Sekiguchi, T., Doi, T., Takahashi, T., Akasaka, K., Rudel, L.L., Tomoda, H., Omura, S.
    • Journal Title

      Journal of Organic Chemistry 71

      Pages: 7643-7649

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Chiral Discrimination of Primary Amins by HPLC After Labeling with a Chiral Derivatization Reagent, trans-2-(2,3-Anthracenedicarbox-imido)cyclohexanecarbonyl Chloride2006

    • Author(s)
      Kazuaki Akasaka, Takashi Ohtaki, Hiroshi Ohrui
    • Journal Title

      Journal of Separation Science 29

      Pages: 1390-1398

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Absolute Stereochemistry of Fungal Beauveriolide III and ACAT Inhibitory Activity of Four Stereoisomers2006

    • Author(s)
      Ohshiro, T., Akasaka, K., 他8名
    • Journal Title

      Journal of Organic Chemistry, 71

      Pages: 7643-7649

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Chiral Discrimination of secondary alcohols by both 1H-NMR and HPLC after labeling with a chiral derivatization reagent, 2-(2,3-anthracenedicarboximide)cyclohexane carboxylic Acid2005

    • Author(s)
      Takashi Ohtaki, Kazuaki Akasaka, 他2名
    • Journal Title

      Chirality 17・S1

      Pages: 171-176

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Development of Highly Potent D-Glucosamine-Based Chiral Fluorescent Labeling Reagents and a Microwave-Assisted β-Selective Glycosidation of a Methyl Glycoside Reagent2005

    • Author(s)
      Hiroshi Ohrui, Kazuaki Akasaka, 他4名
    • Journal Title

      Bioscience, Biotechnology and Boichemistry 69・5

      Pages: 1054-1057

    • NAID

      130000030345

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Crystalline structure of N-(S)-2-heptyl (1R,2R)-2-(2,3-anthracenedicarboximido)cyclohexanecarboxamide that differs from its preferred conformation in the solvent used for crystallization2005

    • Author(s)
      Kazuaki Akasaka, Takashi Ohtaki, 他2名
    • Journal Title

      Bioscience, Biotechnology and Boichemistry 69・10

      Pages: 2002-2004

    • NAID

      130000030540

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthesis of four stereoisomers of 2,6-dimethyloctane-1,8-dioic acid, a component of the copulation release pheromone of the cowpea weevil, Callosobruchus maculates2005

    • Author(s)
      Tomonori Nakai, Arata Yajima, Kazuaki Akasaka, 他5名
    • Journal Title

      Bioscience, Biotechnology and Boichemistry 69・12

      Pages: 2401-2408

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary 2005 Annual Research Report
  • [Journal Article] Chiral Discrimination of secondary alcohols by both ^1H-NMR and HPLC after labeling with a chiral derivatization reagent, 2-(2,3-anthracenedi-carboximide)cyclohexane carboxylic Acid,2005

    • Author(s)
      Takashi Ohtaki, Kazuaki Akasaka, Chizuko Kabuto, Hiroshi Ohrui
    • Journal Title

      Chirality 17(S1)

      Pages: 171-176

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Development of Highly Potent D-Glucosamine-Based Chiral Fluorescent Labeling Reagents and a Microwave-Assisted β-Selective Glycosidation of a Methyl Glycoside Reagent,2005

    • Author(s)
      Hiroshi Ohrui, Rumiko Katoh, Teruhisa Kodaira, Hiroki Shimizu, Kazuaki Akasaka, Takeshi Kitahara
    • Journal Title

      Bioscience, Biotechnology and Boichemistry 69(5)

      Pages: 1054-1057

    • NAID

      130000030345

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Crystalline structure of N-(S)-2-heptyl (1R,2R)-2-(2,3-anthracenedicarboximido)cyclohexanecarboxamide that differs from its preferred conformation in the solvent used for crystallization2005

    • Author(s)
      Kazuaki Akasaka, Takashi Ohtaki, Chizuko Kabuto, Takeshi Kitahara, Hiroshi Ohrui
    • Journal Title

      Bioscience, Biotechnology and Boichemistry 69(10)

      Pages: 2002-2004

    • NAID

      130000030540

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthesis of four stereoisomers of 2,6-dimethyloctane-1,8-dioic acid, a component of the copulation release pheromone of the cowpea weevil, Callosobruchus maculates2005

    • Author(s)
      Tomonori Nakai, Arata Yajima, Kazuaki Akasaka, Takayuki Kaihoku, Miki Ohtaki, Tomoo Nukada, Hiroshi Ohrui, Goro Yabuta
    • Journal Title

      Bioscience, Biotechnology and Boichemistry 69(12)

      Pages: 2401-2408

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Chiral Discrimination of secondary alcohols by both 1H-NMR and HPLC after labeling with a chiral derivatization reagent, 2-(2,3-anthracenedicarboximide) cyclohexane carboxylic Acid2005

    • Author(s)
      Takashi Ohtaki, Kazuaki Akasaka, 他2名
    • Journal Title

      Chirality 17・S1

      Pages: 171-176

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Development of Highly Potent D-Glucosamine-Based Chiral Fluorescent Labeling Reagents and a Microwave-Assisted beta-Selective Glycosidation of a Methyl Glycoside Reagent2005

    • Author(s)
      Hiroshi Ohrui, Kazuaki Akasaka, 他4名
    • Journal Title

      Bioscience, Biotechnology and Boichemistry 69・5

      Pages: 1054-1057

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Crystalline structure of N-(S)-2-heptyl (1R,2R)-2-(2,3-anthracenedicarboximido)cyclohexanecarboxamide that differs from its preferred conformation in the solvent used for crystallization2005

    • Author(s)
      Takashi Ohtaki, Kazuaki Akasaka, 他2名
    • Journal Title

      Bioscience, Biotechnology and Boichemistry 69・10

      Pages: 2002-2004

    • NAID

      130000030540

    • Related Report
      2005 Annual Research Report

URL: 

Published: 2004-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi