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Development of Acid/Radical Self-Relay Catalysis Based on One-Electron Oxidation of the Conjugate Base

Research Project

Project/Area Number 19K15552
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionTohoku University

Principal Investigator

Kikuchi Jun  東北大学, 薬学研究科, 助教 (20802656)

Project Period (FY) 2019-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2022: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2021: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2020: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2019: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Keywords酸触媒 / カチオン / ラジカル / 光反応 / 不斉反応 / ブレンステッド酸 / 光励起 / ラジカル反応 / 有機分子触媒 / 一電子酸化
Outline of Research at the Start

本研究では、酸触媒の共役塩基が一電子酸化によって、ラジカルへと変換できることに着目し、元来の「酸触媒」としての機能に加えて「ラジカル触媒」としての機能を発現させる。これらをリレー型に活用することで、従来のイオン反応の枠組みから脱した高度分子変換を実現する。共役塩基の一電子酸化は、酸触媒の作用によって生じるカチオン種を光励起させ、一電子酸化剤として機能させる手法ならびに光酸化還元触媒との協同触媒系とすることで行う。

Outline of Final Research Achievements

With the aim of expanding the scope of Bronsted acid-catalyzed reactions, which were generally limited to ionic reactions, we developed radical reactions through the photo-excitation of cationic intermediates, which enables them to function as strong oxidants. As a result, we found that radical reactions involving the C-H functionalization of toluene and alkenes could be achieved by photo-excitation of cationic species such as benzopyrylium and iminium cations. The study provided insights into the reaction mechanism and successfully established chiral Bronsted acid-catalyzed enantioselective radical reactions. In addition, the utilization of silyl Lewis acids and π-acidic metals as catalysts was found to expand the range of excited cationic species accessible.

Academic Significance and Societal Importance of the Research Achievements

本研究で開発した手法は、温和かつメタルフリーな条件下で芳香族炭化水素や単純オレフィンといった安価な炭素資源を光学活性化合物へと変換できるため、環境調和型な分子変換法の開発研究に新たな指針を与えるものとして社会的意義があると考えられる。また本研究は、酸触媒を用いた分子変換プロセスに新たな可能性を示すとともに、未だ報告例が限られている有機分子触媒による不斉ラジカル反応を実現した点で学術的に意義がある。

Report

(5 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Research-status Report
  • 2020 Research-status Report
  • 2019 Research-status Report
  • Research Products

    (7 results)

All 2023 2022 2021 2020 2019

All Journal Article (3 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 3 results) Presentation (4 results) (of which Int'l Joint Research: 1 results)

  • [Journal Article] Site‐Selective C-H Alkenylation of N‐Heteroarenes by Ligand‐Directed Co/Al and Co/Mg Cooperative Catalysis**2023

    • Author(s)
      Saito Yuri、Kikuchi Jun、Wang Chen、Yoshikai Naohiko
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 62 Issue: 17

    • DOI

      10.1002/anie.202301006

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Stereoselective Synthesis of β-Alkoxy-β-amido Vinylbenziodoxoles via Iodo(III)etherification of Ynamides2022

    • Author(s)
      Kikuchi Jun、Maesaki Kaito、Sasaki Shuma、Wang Weifan、Ito Shingo、Yoshikai Naohiko
    • Journal Title

      Organic Letters

      Volume: 24 Issue: 38 Pages: 6914-6918

    • DOI

      10.1021/acs.orglett.2c02570

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Radical addition reaction between chromenols and toluene derivatives initiated by Brensted acid catalyst under light irradiation2021

    • Author(s)
      Jun Kikuchi, Shota Kodama, Masahiro Terada
    • Journal Title

      Organic Chemistry Frontiers

      Volume: 8 Issue: 15 Pages: 4153-4159

    • DOI

      10.1039/d1qo00657f

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Presentation] Stereoselective Synthesis of β-Alkoxy-β-amido Vinylbenziodoxoles via Iodo(III)etherification of Ynamides2022

    • Author(s)
      Kikuchi Jun
    • Organizer
      ISXB5 5th international symposium on halogen bonding
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Brnsted Acid-Catalyzed Radical Addition Reaction between Toluene Derivatives and Chromenols under Light Irradiation2020

    • Author(s)
      菊池隼
    • Organizer
      令和2年度化学系学協会東北大会
    • Related Report
      2020 Research-status Report
  • [Presentation] ベンゾピリリウムカチオン中間体を一電子酸化剤として利用したブレンステッド酸触媒によるトルエン誘導体のC-H官能基化反応の開発2020

    • Author(s)
      菊池隼
    • Organizer
      日本化学会 第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Bronsted Acid-Catalyzed C-H Functionalization of Toluene Derivatives Utilizing Benzopyrylium Cation Intermediate as a Strong Oxidant under Light Irradiation2019

    • Author(s)
      菊池隼
    • Organizer
      第12回 有機触媒シンポジウム
    • Related Report
      2019 Research-status Report

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Published: 2019-04-18   Modified: 2024-01-30  

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