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Evaluation of nitroxide radical catalyst activity in the C-H activation step of the oxidative coupling between acridone derivatives and nitromethane

Research Project

Project/Area Number 26810055
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Synthetic chemistry
Research InstitutionYokohama National University

Principal Investigator

Gotoh Hiroaki  横浜国立大学, 大学院工学研究院, 准教授 (80635235)

Project Period (FY) 2014-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2016: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2015: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Fiscal Year 2014: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Keywords有機分子触媒 / ラジカル / 反応機構解析 / ニトロキシドラジカル / 酸素 / カップリング反応 / フロー反応 / 有機合成化学 / 酸化的カップリング / TEMPO / 環境調和型 / グリーンケミストリー
Outline of Final Research Achievements

Organocatalysts have been the subject of intense research effort because of their low toxicity, facile handling, and eco-friendly characteristics. Recently, the development of the C-H activation reaction using organocatalysts has also been studied. We report studies on the oxidative coupling of acridone and nitromethane using a range of radicals. BPAN (tert-butyl(10-phenyl-9-anthryl)nitroxide) was found to be an optimal catalyst for the coupling reaction. It has been considered that in the hydrogen abstraction reaction, the values of the LUMO on the oxygen atom are particularly important. In addition, upon reoxidation to increase catalyst efficiency, the value of the HOMO orbital of the NO-H moiety on the reductant is also important. BPAN was demonstrated to be the optimal radical with regards to all of these values.

Report

(4 results)
  • 2016 Annual Research Report   Final Research Report ( PDF )
  • 2015 Research-status Report
  • 2014 Research-status Report
  • Research Products

    (9 results)

All 2016 2015 2014

All Journal Article (3 results) (of which Peer Reviewed: 3 results,  Acknowledgement Compliant: 1 results) Presentation (6 results)

  • [Journal Article] Trapping chlorine radicals via substituting nitro radicals in the gas phase2016

    • Author(s)
      Akira Seto, Yuki Ochi, Hiroaki Gotoh, Kazuhisa Sakakibara, Shota Hatazawa, Kanekazu Seki, Naoaki Saito, Yuji Mishima
    • Journal Title

      Analytical Methods

      Volume: 8 Issue: 1 Pages: 25-28

    • DOI

      10.1039/c5ay01118c

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Novel degradation mechanism for triarylmethane dyes: Acceleration of degradation speed by the attack of active oxygen to halogen groups2016

    • Author(s)
      Sarara. Nakagawa, Kazuhisa. Sakakibara, Hiroaki Gotoh
    • Journal Title

      Dyes and Pigments

      Volume: 124 Pages: 130-132

    • DOI

      10.1016/j.dyepig.2015.09.006

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Journal Article] Previous Article Next Article Table of Contents Scavenging and Characterization of Short-Lived Radicals Using a Novel Stable Nitroxide Radical with a Characteristic UV–vis Absorption Spectrum2014

    • Author(s)
      Ryuta Toba , Hiroaki Gotoh *, and Kazuhisa Sakakibara
    • Journal Title

      Organic Letters

      Volume: 16 Issue: 15 Pages: 3868-3871

    • DOI

      10.1021/ol501328k

    • Related Report
      2014 Research-status Report
    • Peer Reviewed
  • [Presentation] 生理活性物質Curcuphenolの全合成ーラジカル反応を利用した直接的酸化反応ー2016

    • Author(s)
      〇笹田良介・五東弘昭・榊原和久
    • Organizer
      第51回天然物化学談話会
    • Place of Presentation
      湯沢東映ホテル
    • Year and Date
      2016-07-06
    • Related Report
      2016 Annual Research Report
  • [Presentation] 機能性物質への組み込みを利用したニトロキシドラジカルの合成2016

    • Author(s)
      〇笹岡佑裕・五東弘昭・榊原和久
    • Organizer
      第51回天然物化学談話会
    • Place of Presentation
      湯沢東映ホテル
    • Year and Date
      2016-07-06
    • Related Report
      2016 Annual Research Report
  • [Presentation] ニトロキシドラジカルを触媒とした酸化的C-C結合形成反応における新規有機分子触媒の開拓2015

    • Author(s)
      岩崎浩介、浜田拓実、五東弘昭、榊原和久
    • Organizer
      第69回有機合成化学協会関東シンポジウム
    • Place of Presentation
      横浜国立大学
    • Year and Date
      2015-05-16
    • Related Report
      2015 Research-status Report
  • [Presentation] ニトロキシルラジカルを触媒とした酸化的C-C結合形成反応における新規有機分子触媒の開拓2015

    • Author(s)
      ○岩崎浩介、浜田拓実、五東弘昭、榊原和久
    • Organizer
      第69回有機合成化学協会関東支部シンポジウム
    • Place of Presentation
      横浜国立大学
    • Year and Date
      2015-05-16
    • Related Report
      2014 Research-status Report
  • [Presentation] 新規特異的UV-vis吸収スペクトルを有するニトロキシルラジカルを用いた短寿命活性ラジカル種の捕獲と 同定2014

    • Author(s)
      ○五東弘昭・鳥羽隆太・榊原和久
    • Organizer
      第25回基礎有機化学討論会
    • Place of Presentation
      東北大学
    • Year and Date
      2014-09-07
    • Related Report
      2014 Research-status Report
  • [Presentation] アクリドン誘導体とニトロメタンとの酸化的カップリング反応におけるニトロキシルラジカルの触媒能評 価2014

    • Author(s)
      ○岩崎浩介・五東弘昭・榊原和久
    • Organizer
      第25回基礎有機化学討論会
    • Place of Presentation
      東北大学
    • Year and Date
      2014-09-07
    • Related Report
      2014 Research-status Report

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Published: 2014-04-04   Modified: 2018-03-22  

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