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反応集積化によるフッ素系中分子化合物の高選択的合成と新機能開発

Publicly Offered Research

Project AreaMiddle molecular strategy: Creation of higher bio-functional molecules by integrated synthesis.
Project/Area Number 16H01129
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionGunma University

Principal Investigator

網井 秀樹  群馬大学, 大学院理工学府, 教授 (00284084)

Project Period (FY) 2016-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥5,720,000 (Direct Cost: ¥4,400,000、Indirect Cost: ¥1,320,000)
Fiscal Year 2017: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Fiscal Year 2016: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Keywords反応集積化 / フッ素 / カルボアニオン / ラジカル / フローマイクロリアクター / 中分子 / フルオロアルキル化 / フッ素化リン脂質
Outline of Annual Research Achievements

有機フッ素化合物は、フッ素原子が醸し出す特異な性質により、医薬・農薬、並びに液晶等の機能性材料として注目を浴びている。トリフルオロメチル基などの含フッ素官能基の有機化合物への導入は、有機フッ素化合物合成における基幹技術である。特に、「求核的、およびラジカル的含フッ素官能基導入反応」は、合成化学的に汎用性が高いため、多岐に渡るフッ素化合物の合成に対し強力な手法である。一般的に、α位にフッ素を有するカルバニオン種は、発生が困難であり、不安定である。フフッ素系中分子化合物の新しい合成法の開発を目指して,含フッ素カルボアニオン種,ラジカル種の反応を開発する.シリル基によって安定化された含フッ素カルボアニオンの発生とその反応を研究している.フッ化ベンジルにより容易に得られるα-シリルフッ化ベンジルに,塩基存在下で塩化トリエチルシリルを作用させると,ベンジル位に異種のシリル基(TMSとTES)を有する含フッ素化合物が得られた.α-フルオロ-α-シリルベンジルアニオン種とヨウ化イソプロピルとの反応が進行し,その結果,フルオロメチルベンゼンのベンジル位に複数の置換基を導入することが可能となった.さらに、フッ素化リン脂質骨格を有する中分子化合物の高選択的合成への応用を目指し,マイクロフロー法による高効率的ラジカル付加反応を進めている。実際に、ヨウ化ペルフルオロアルキルのアルケンへの付加反応において、反応の高速化、および制御の観点からフローマイクロリアクターの利用が非常に有効であることがわかった。

Research Progress Status

29年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

29年度が最終年度であるため、記入しない。

Report

(2 results)
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • Research Products

    (35 results)

All 2018 2017 2016 Other

All Int'l Joint Research (3 results) Journal Article (8 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 8 results,  Open Access: 3 results,  Acknowledgement Compliant: 3 results) Presentation (24 results) (of which Int'l Joint Research: 11 results,  Invited: 7 results)

  • [Int'l Joint Research] University of Louisville(米国)

    • Related Report
      2017 Annual Research Report
  • [Int'l Joint Research] Universitat de Valencia(スペイン)

    • Related Report
      2017 Annual Research Report
  • [Int'l Joint Research] Universitat de Valencia(スペイン)

    • Related Report
      2016 Annual Research Report
  • [Journal Article] A Convenient Method for Catalytic Aromatic Pentafluoroethylation Using Potassium (Pentafluoroethyl)trimethoxyborate2017

    • Author(s)
      Tsuyuka Sugiishi, Daisuke Kawauchi, Mizuki Sato, Tatsuya Sakai, Hideki Amii
    • Journal Title

      Synthesis

      Volume: 49 Issue: 08 Pages: 1874-1878

    • DOI

      10.1055/s-0036-1589477

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Study of Perfluoroalkyl Chain-Specific Band Shift in Infrared Spectra on the Chain Length2017

    • Author(s)
      Shimoaka Takafumi、Sonoyama Masashi、Amii Hideki、Takagi Toshiyuki、Kanamori Toshiyuki、Hasegawa Takeshi
    • Journal Title

      The Journal of Physical Chemistry A

      Volume: 121 Issue: 44 Pages: 8425-8431

    • DOI

      10.1021/acs.jpca.7b08940

    • NAID

      120006364087

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Predicting Counterion Effects Using a Gold Affinity Index and a Hydrogen Bonding Basicity Index2017

    • Author(s)
      Zhichao Lu, Junbin Han, Otome Okoromoba, Naoto Shimizu, Hideki Amii, Hideki; Claudio Tormena, Gerald B. Hammond, Bo Xu
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 21 Pages: 5848-5851

    • DOI

      10.1021/acs.orglett.7b02829

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Enolate-Based Strategies to Construct <i>gem</i>-Difluoromethylene Compounds2017

    • Author(s)
      Hideki Amii
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 75 Issue: 11 Pages: 1125-1132

    • DOI

      10.5059/yukigoseikyokaishi.75.1125

    • NAID

      130006196250

    • ISSN
      0037-9980, 1883-6526
    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] 便利!汎用試薬を使うトリフルオロメチル化反応2017

    • Author(s)
      杉石露佳, 網井秀樹
    • Journal Title

      月刊「化学」

      Volume: 72 Pages: 1125-1132

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Trifluoromethylation of Aryl Iodides Catalyzed by the Copper(I)-Phen Complex2016

    • Author(s)
      Naoto Shimizu, Hideaki Kondo, Masahiro Oishi, Kenichi Fujikawa, Kazuki Komoda, and Hideki Amii
    • Journal Title

      Organic Syntheses

      Volume: 93 Pages: 147-162

    • DOI

      10.15227/orgsyn.093.0147

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Lateral Diffusion and Molecular Interaction in a Bilayer Membrane Consisting of Partially Fluorinated Phospholipids2016

    • Author(s)
      Y. Okamoto, T. Motegi, K. Morita, T. Takagi, H. Amii, T. Kanamori, M. Sonoyama, R. Tero
    • Journal Title

      Langmuir

      Volume: 32 Issue: 41 Pages: 10712-10718

    • DOI

      10.1021/acs.langmuir.6b02874

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Surface Properties of a Single Perfluoroalkyl Group on Water Surfaces Studied by Surface Potential Measurements2016

    • Author(s)
      Takafumi Shimoaka, Yuki Tanaka, Nobutaka Shioya, Kohei Morita, Masashi Sonoyama, Hideki Amii, Toshiyuki Takagi, Takeshi Hasegawa
    • Journal Title

      J. Colloid Interface Sci.

      Volume: 483 Pages: 353-359

    • DOI

      10.1016/j.jcis.2016.08.055

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed
  • [Presentation] Generation and Reactions of 2,2,2-Trifluoro-1-(phenylsulfonyl)ethyl Anion2018

    • Author(s)
      Ryosuke Arai, Yoshiyuki Murata, Aiichiro Nagaki, Junichi Yoshida, Hideki Amii
    • Organizer
      The First International Conference on Automated Flow and Microreactor Synthesis (ICAMS-1)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Generation and Synthetic Applications of Trifluoromethyl Isobenzofurans2018

    • Author(s)
      Shun Shinada, Masanori Inaba, Yoshimasa Hikobe, Yuta Nishina, and Hideki Amii
    • Organizer
      The First International Conference on Automated Flow and Microreactor Synthesis (ICAMS-1)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 有機フッ素化合物の合成法開発と18F放射性医薬の創製・臨床応用の新展開2018

    • Author(s)
      網井秀樹
    • Organizer
      日本学術振興会フッ素化学第155委員会第111回研究会
    • Related Report
      2017 Annual Research Report
  • [Presentation] マイクロフロー法によるラジカル的ペルフルオロアルキル化の反応制御2018

    • Author(s)
      渡部鯨波, 新井椋介, 園山正史, 網井秀樹
    • Organizer
      日本化学会第98春季年会2018
    • Related Report
      2017 Annual Research Report
  • [Presentation] フッ素化ベンゾシクロブテノン誘導体の合成と反応2018

    • Author(s)
      小茂田和希,田中惟吹,杉石露佳,網井秀樹
    • Organizer
      日本化学会第98春季年会2018
    • Related Report
      2017 Annual Research Report
  • [Presentation] α-フルオロベンジルジアニオン等価体の反応2018

    • Author(s)
      田上祐太, 北原拓, 小野雅樹, 杉石露佳, 松原誠二郎, 網井秀樹
    • Organizer
      日本化学会第98春季年会2018
    • Related Report
      2017 Annual Research Report
  • [Presentation] 芳香族モノフルオロメチル化合物のラジカル的変換反応2017

    • Author(s)
      下川あい,上山晃平,森岡亮,杉石露佳,網井秀樹
    • Organizer
      第6回 JACI/GSCシンポジウム
    • Related Report
      2017 Annual Research Report
  • [Presentation] Recent Progress in Catalytic Aromatic Fluoroalkylation2017

    • Author(s)
      Hideki Amii
    • Organizer
      The 8th International Meeting on Halogen Chemistry (HALCHEM VIII)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Generation and Reactions of 2,2,2-Trifluoro-1-(phenylsulfonyl)ethyl Carbanion2017

    • Author(s)
      Ryosuke Arai, Yoshiyuki Murata, Aiichiro Nagaki, Junichi Yoshida, Hideki Amii
    • Organizer
      The 8th International Meeting on Halogen Chemistry (HALCHEM VIII)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 急進展する有機フッ素化合物の合成法2017

    • Author(s)
      網井秀樹
    • Organizer
      第15回有機合成化学談話会
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] ホウ素反応剤を用いる触媒的芳香族ペンタフルオロエチル化2017

    • Author(s)
      杉石露佳, 河内大佑, 佐藤瑞記, 坂井達也, 網井秀樹
    • Organizer
      第35回メディシナルケミストリーシンポジウム
    • Related Report
      2017 Annual Research Report
  • [Presentation] アリールジフルオロメチルアニオン種の不飽和エステルへの共役付加反応2017

    • Author(s)
      甲谷渉, 杉石露佳, 網井秀樹
    • Organizer
      第40回フッ素化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Fluoroalkylation/Cyclization Route to Fluorinated Phthalides2017

    • Author(s)
      Masanori Inaba, Tatsuya Sakai, Shun Shinada, Tsuyuka Sugiishi, Yuta Nishina, Norio Shibata, Hideki Amii
    • Organizer
      The 11th International Symposium on Integrated Synthesis (ISONIS-11)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] フローマイクロリアクターを用いた2,2,2-トリフルオロ-1-(フェニルスルホニル)エチルアニオンの精密反応制御2017

    • Author(s)
      新井椋介, 網井秀樹, 村田啓幸, 永木愛一郎, 吉田潤一
    • Organizer
      日本化学会第97春季年会
    • Related Report
      2016 Annual Research Report
  • [Presentation] アリールジフルオロメチルアニオン種を用いる炭素-炭素結合形成反応2017

    • Author(s)
      甲谷渉, 杉石露佳, 網井秀樹
    • Organizer
      日本化学会第97春季年会
    • Related Report
      2016 Annual Research Report
  • [Presentation] A Convenient Decarboxylative Route to Difluoromethylene Compounds2016

    • Author(s)
      Hideki Amii
    • Organizer
      The 12th International Symposium on Organic Reactions (ISOR-12)
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Highly Controlled Nucleophilic Aromatic Substitution Using a Flow Microreactor2016

    • Author(s)
      Aya Takano, Yoshiyuki Murata, and Hideki Amii
    • Organizer
      The 12th International Symposium on Organic Reactions (ISOR-12)
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Selective Synthesis of gem-Difluoromethylene Compounds2016

    • Author(s)
      Hideki Amii
    • Organizer
      18th European Symposium on Fluorine Chemistry
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] β-炭素脱離による触媒的芳香族トリフルオロメチル化と,ペンタフルオロエチル化2016

    • Author(s)
      小茂田和希, 久保田結衣, 杉石露佳, 芹澤宏希, 相川光介, 三上幸一, 網井秀樹
    • Organizer
      第6回フッ素化学若手の会
    • Related Report
      2016 Annual Research Report
  • [Presentation] Recent Progress in Catalytic Aromatic Trifluoromethylation2016

    • Author(s)
      Hideki Amii
    • Organizer
      3rd International Conference on Past and Present Research Systems of Green Chemistry
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Generation and Reactions of Aryldifluoromethyl Radicals2016

    • Author(s)
      Kouhei Ueyama, Ryou Kasuga, Hitomi Kimura, Tsuyuka Sugiishi, and Hideki Amii
    • Organizer
      The 10th International Symposium on Integrated Synthesis (ISONIS-10)
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Recent Progress in Nucleophilic Fluoroalkylations2016

    • Author(s)
      Hideki Amii
    • Organizer
      14th National Meeting on Fluorine Chemistry, China
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 触媒的芳香族トリフルオロメチル化と関連反応の開発2016

    • Author(s)
      網井秀樹
    • Organizer
      最新化学談話シリーズ(九州大学)
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] フッ素化ベンゾシクロブテノン類の合成と反応2016

    • Author(s)
      小茂田和希, 杉石露佳, 網井秀樹
    • Organizer
      平成28年度日本化学会関東支部群馬地区研究交流発表会
    • Related Report
      2016 Annual Research Report

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Published: 2016-04-26   Modified: 2022-02-28  

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