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Advanced utilization of multiple short-lived reactive species by application of flash flow electrolysis

Research Project

Project/Area Number 20K15276
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionHokkaido University (2022)
Kyoto University (2020-2021)

Principal Investigator

Yosuke Ashikari  北海道大学, 理学研究院, 特任助教 (70865584)

Project Period (FY) 2020-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2022: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2021: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2020: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywordsフロー反応 / 電解反応 / 不安定中間体 / 電解合成 / カルボカチオン / 電極反応 / 不安定活性種 / カチオンフロー法 / 有機カチオン / フローマイクロ合成
Outline of Research at the Start

電極反応は不安定活性種を不可逆的に発生できる特徴的な形式の反応である。しかし生じた中間体(例えば炭素カチオン種)は不安定であり、合成的な活用は限定的である。
本研究では、カチオン種など極めて不安定な中間体(例えば寿命1秒程度)を短時間で発生可能なフローマイクロ電解装置の開発を行う。さらに不安定中間体の高次な活用を基軸として、複数の活性種を経由する新規分子変換手法の開発を行う。最終的にはフローマイクロ電解装置の両極を活用する。すなわち酸化側でカチオン性中間体を発生させ、同時に還元側でアニオン性中間体を発生させるなど、生体内を模倣した分子変換プロセスの構築を最終目標とする。

Outline of Final Research Achievements

The purpose of this project is to develop a novel flow electrosynthesis devise enabling the generation and reactions of unstable reactive intermediates, and to develop a novel reactions by means of the electrosynthesis devise. With a thorough screening for a material of electrode and its shape, and the path, we established the new flow electrosynthesis devise which allows a rapid electro-oxidation reaction in flow. Additionally, we achieved the generation of a kind of carbocations, including glycosyl cations, and their reactions in flow.

Academic Significance and Societal Importance of the Research Achievements

本研究では、近年世界的に注目を集めている電解合成において、従来技術では不可能な「高速な合成」を可能にするデバイスの開発とそのデバイスを用いた合成反応の開発を行った。電解反応は電極表面で進行するため、通常のデバイスでの反応は時間を要する。しかし不安定な中間体を生じる電解合成では、反応中に徐々に中間体が分解してしまう。本研究で開発したフロー電解装置では、数秒単位のごく短い時間で速やかに電解反応が可能であり、これを活用することで、極めて不安定な化学種の発生とその合成利用が可能である。

Report

(4 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Research-status Report
  • 2020 Research-status Report
  • Research Products

    (22 results)

All 2023 2022 2021 2020 Other

All Int'l Joint Research (1 results) Journal Article (13 results) (of which Peer Reviewed: 13 results,  Open Access: 4 results) Presentation (4 results) (of which Int'l Joint Research: 1 results) Book (4 results)

  • [Int'l Joint Research] University of Pavia(イタリア)

    • Related Report
      2022 Annual Research Report
  • [Journal Article] Flash functional group-tolerant biaryl-synthesis based on integration of lithiation, zincation and negishi coupling in flow2022

    • Author(s)
      Ashikari Yosuke、Guan Kaiteng、Nagaki Aiichiro
    • Journal Title

      Frontiers in Chemical Engineering

      Volume: 4 Pages: 964767-964767

    • DOI

      10.3389/fceng.2022.964767

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Investigation of Parameter Control for Electrocatalytic Semihydrogenation in a Proton-Exchange Membrane Reactor Utilizing Bayesian Optimization2022

    • Author(s)
      Ashikari Yosuke、Tamaki Takashi、Takahashi Yusuke、Yao Yiyue、Atobe Mahito、Nagaki Aiichiro
    • Journal Title

      Frontiers in Chemical Engineering

      Volume: 3 Pages: 819752-819752

    • DOI

      10.3389/fceng.2021.819752

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] フローマイクロケミストリーに基づく反応集積化2022

    • Author(s)
      永木愛一郎、芦刈洋祐
    • Journal Title

      ケミカルタイムス

      Volume: 263 Pages: 3-6

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Flow grams-per-hour production enabled by hierarchical bimodal porous silica gel supported palladium column reactor having low pressure drop2022

    • Author(s)
      Ashikari Yosuke、Maekawa Kei、Takumi Masahiro、Tomiyasu Noriyuki、Fujita Chiemi、Matsuyama Kiyoshi、Miyamoto Riichi、Bai Hongzhi、Nagaki Aiichiro
    • Journal Title

      Catalysis Today

      Volume: 388-389 Pages: 231-236

    • DOI

      10.1016/j.cattod.2020.07.014

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Homogeneous Catalyzed Aryl?Aryl Cross-Couplings in Flow2021

    • Author(s)
      Nagaki Aiichiro、Ashikari Yosuke
    • Journal Title

      Synthesis

      Volume: 53 Issue: 11 Pages: 1879-1888

    • DOI

      10.1055/a-1360-7798

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Switchable Chemoselectivity of Reactive Intermediates Formation and Their Direct Use in A Flow Microreactor2021

    • Author(s)
      Ashikari Yosuke、Tamaki Takashi、Kawaguchi Tomoko、Furusawa Mai、Yonekura Yuya、Ishikawa Susumu、Takahashi Yusuke、Aizawa Yoko、Nagaki Aiichiro
    • Journal Title

      Chemistry A European Journal

      Volume: 27 Issue: 65 Pages: 16107-16111

    • DOI

      10.1002/chem.202103183

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Stille, Heck, and Sonogashira coupling and hydrogenation catalyzed by porous-silica-gel-supported palladium in batch and flow2021

    • Author(s)
      Ashikari Yosuke、Maekawa Kei、Ishibashi Mai、Fujita Chiemi、Shiosaki Kiyonari、Bai Hongzhi、Matsuyama Kiyoshi、Nagaki Aiichiro
    • Journal Title

      Green Processing and Synthesis

      Volume: 10 Issue: 1 Pages: 722-728

    • DOI

      10.1515/gps-2021-0069

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] フロー高速合成とAI活用の将来展望について2021

    • Author(s)
      永木愛一郎、芦刈洋祐、宅見正浩
    • Journal Title

      化学工学

      Volume: 85 Pages: 611-614

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Multiple Organolithium Reactions for Drug Discovery Using Flash Chemistry2021

    • Author(s)
      Ashikari Yosuke、Tamaki Takashi、Takumi Masahiro、Nagaki Aiichiro
    • Journal Title

      Topics in Medicinal Chemistry

      Volume: 0 Pages: 223-239

    • DOI

      10.1007/7355_2021_113

    • ISBN
      9783030855918, 9783030855925
    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Flash Chemistry Makes Impossible Organolithium Chemistry Possible2021

    • Author(s)
      Aiichiro Nagaki, Yosuke Ashikari, Masahiro Takumi, Takashi Tamaki
    • Journal Title

      Chemistry Letters

      Volume: 50 Issue: 3 Pages: 485-492

    • DOI

      10.1246/cl.200837

    • NAID

      130007995528

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] A Synthetic Approach to Dimetalated Arenes Using Flow Microreactors and the Switchable Application to Chemoselective Cross-Coupling Reactions2020

    • Author(s)
      Yosuke Ashikari, Tomoko Kawaguchi, Kyoko Mandai, Yoko Aizawa, Aiichiro Nagaki
    • Journal Title

      Journal of American Chemical Society

      Volume: 142 Issue: 40 Pages: 17039-17047

    • DOI

      10.1021/jacs.0c06370

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Accelerating Heat-Initiated Radical Reactions of Organic Halides with Tin Hydride Using Flow Microreactor Technologies2020

    • Author(s)
      Yiyuan Jiang, Yosuke Ashikari, Kaiteng Guan, Aiichiro Nagaki
    • Journal Title

      Synlett

      Volume: 31 Issue: 19 Pages: 1937-1941

    • DOI

      10.1055/s-0040-1707307

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Pd catalysts supported on dual-pore monolithic silica beads for chemoselective hydrogenation under batch and flow reaction conditions2020

    • Author(s)
      Yamada Tsuyoshi、Ogawa Aya、Masuda Hayato、Teranishi Wataru、Fujii Akiko、Park Kwihwan、Ashikari Yosuke、Tomiyasu Noriyuki、Ichikawa Tomohiro、Miyamoto Riichi、Bai Hongzhi、Matsuyama Kiyoshi、Nagaki Aiichiro、Sajiki Hironao
    • Journal Title

      Catalysis Science & Technology

      Volume: 10 Issue: 18 Pages: 6359-6367

    • DOI

      10.1039/d0cy01442g

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Presentation] 高速電解フローリアクターによるグリコシルカチオン種の発生とO-C転位の制御2023

    • Author(s)
      姚弋越、宅見正浩、芦刈洋祐、永木愛一郎
    • Organizer
      日本化学会第103年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Flow micro synthesis based on generation and reactions of aryllithiums bearing highly-coordinated anionic functionalities2021

    • Author(s)
      Yosuke Ashikari, Daisuke Ichinari, Kyoko Mandai, Tomoko Kawaguchi, Yoko Aizawa, Aiichiro Nagaki
    • Organizer
      The 2021 International Chemical Congress of Pacific Basin Societies (Pacifichem 2021)
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research
  • [Presentation] 高配位アニオン性置換基を活用するバイメタリックアレーン類のフローマイクロ合成2021

    • Author(s)
      川口倫子、芦刈洋祐、萬代恭子、相澤瑤子、永木愛一郎
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Research-status Report
  • [Presentation] フローマイクロリアクターにより合成したバイメタリックアレーン類の化学選択的カップリング反応2021

    • Author(s)
      芦刈洋祐、川口倫子、萬代恭子、相澤瑤子、永木愛一郎
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Research-status Report
  • [Book] マイクロ・ナノ熱工学の進展2021

    • Author(s)
      マイクロ・ナノ熱工学の進展編集委員会、丸山 茂夫、稲田 孝明ほか17名
    • Total Pages
      808
    • Publisher
      エヌ・ティー・エス
    • ISBN
      9784860437220
    • Related Report
      2021 Research-status Report 2020 Research-status Report
  • [Book] フローマイクロ合成の最新動向2021

    • Author(s)
      深瀬浩一、永木愛一郎
    • Total Pages
      250
    • Publisher
      シーエムシー出版
    • ISBN
      9784781316154
    • Related Report
      2021 Research-status Report
  • [Book] フロー合成、連続生産のプロセス設計、条件設定と応用事例2020

    • Author(s)
      芦刈洋祐ほか
    • Total Pages
      599
    • Publisher
      技術情報協会
    • ISBN
      9784861048203
    • Related Report
      2020 Research-status Report
  • [Book] マイクロリアクター/フロー合成による反応条件を最適化した導入と目的に応じた実生産への適用2020

    • Author(s)
      芦刈洋祐ほか
    • Total Pages
      270
    • Publisher
      サイエンス&テクノロジー社
    • ISBN
      9784864282116
    • Related Report
      2020 Research-status Report

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Published: 2020-04-28   Modified: 2024-01-30  

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