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Design and Application of Zwitterionic Triazolium Amidate as Hydrogen-Atom Transfer Catalyst

Research Project

Project/Area Number 18H01972
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionNagoya University

Principal Investigator

Ohmatsu Kohsuke  名古屋大学, 工学研究科(WPI), 特任准教授 (00508997)

Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥17,550,000 (Direct Cost: ¥13,500,000、Indirect Cost: ¥4,050,000)
Fiscal Year 2020: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2019: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2018: ¥7,410,000 (Direct Cost: ¥5,700,000、Indirect Cost: ¥1,710,000)
Keywords有機分子触媒 / 水素原子移動 / 光レドックス触媒 / 双性イオン / 1,2,3-トリアゾール / 触媒開発 / ラジカル触媒反応 / ラジカル / イオン性分子触媒 / 水素原子移動反応 / 選択的触媒反応
Outline of Final Research Achievements

The catalysis for hydrogen-atom transfer (HAT) is a powerful tool for the direct conversion of inert C-H bonds to C-C bonds. We have designed a zwitterionic 1,2,3-triazolium amidate as an effective modular hydrogen-atom transfer catalyst for photoredox C-H functionalization. This zwitterionic amidate is stable yet amenable to single-electron oxidation for generating a highly reactive amidyl radical. By the combined use with an appropriate Ir-based visible-light photoredox catalyst, we have accomplished efficient catalytic C-H alkylation of a range of C-H nucleophiles. These results provide the new approach to the design of HAT catalysts, and we believe that the judicious exploitation of the structural modularity of zwitterionic amidates holds vast potential for the development of catalyst-controlled selective C-H functionalization methodologies.

Academic Significance and Societal Importance of the Research Achievements

有機分子に遍在する炭素-水素結合を切断し、任意の官能基に変換する手法は、効率的な物質生産の実現に貢献する重要な化学技術である。本研究で開発したトリアゾリウムアミデートによる水素原子移動反応や、メソリティック開裂の能動的制御によるシリルエノールエーテル類のアリル位炭素-水素結合変換反応は、反応基質に存在する極性官能基を残したまま比較的安定な炭素-水素結合を官能基化できるという特徴をもつ。合成化学の分野で長足の進歩を遂げてきた極性反応と組み合わせることで、単純な原料から複雑な化合物を効率的に合成する道を切り拓いたという点に、本研究成果の意義がある。

Report

(4 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • Research Products

    (23 results)

All 2021 2020 2019

All Journal Article (7 results) (of which Peer Reviewed: 7 results,  Open Access: 1 results) Presentation (16 results) (of which Int'l Joint Research: 2 results)

  • [Journal Article] Exploiting Transient Radical Cations as Bronsted Acids for Allylic C-H Heteroarylation of Enol Silyl Ethers2021

    • Author(s)
      Tsubasa Nakashima, Haruka Fujimori, Kohsuke Ohmatsu, Takashi Ooi
    • Journal Title

      Chem. Eur. J.

      Volume: - Issue: 36 Pages: 9253-9256

    • DOI

      10.1002/chem.202101352

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ion-paired Ligands for Palladium-catalyzed Allylic Alkylation under Base-free Conditions2020

    • Author(s)
      Kohsuke Ohmatsu, Naho Matsuyama, Yuya Nagato, Takashi Ooi
    • Journal Title

      Chem. Lett.

      Volume: 49 Issue: 9 Pages: 1114-1116

    • DOI

      10.1246/cl.200264

    • NAID

      130007897089

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Mannich-type allylic C-H functionalization of enol silyl ethers under photoredox-thiol hybrid catalysis2020

    • Author(s)
      Tsubasa Nakashima, Kohsuke Ohmatsu, Takashi Ooi
    • Journal Title

      Org. Biomol. Chem.

      Volume: 19 Issue: 1 Pages: 141-145

    • DOI

      10.1039/d0ob01862g

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hybrid Catalysis of 8-Quinolinecarboxaldehyde and Bronsted Acid for Efficient Racemization of α-Amino Amides and Its Application in Chemoenzymatic Dynamic Kinetic Resolution2020

    • Author(s)
      Kohsuke Ohmatsu, Mari Kiyokawa, Yuto Shirai, Yuya Nagato, Takashi Ooi
    • Journal Title

      Heterocycles

      Volume: 103 Issue: 1 Pages: 218-224

    • DOI

      10.3987/com-20-s(k)32

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Zwitterionic 1,2,3-Triazolium Amidate as a Catalyst for Photoinduced Hydrogen-Atom Transfer Radical Alkylation2020

    • Author(s)
      Kohsuke Ohmatsu, Ryuhei Suzuki, Yukino Furukawa, Makoto Sato, and Takashi Ooi
    • Journal Title

      ACS Catal.

      Volume: 10 Issue: 4 Pages: 2627-2632

    • DOI

      10.1021/acscatal.9b04491

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Non‐Enzymatic Hybrid Catalysis for Stereoconversion of l-Amino Acid Derivatives to d-Isomers2020

    • Author(s)
      Yuya Nagato, Mari Kiyokawa, Yusuke Ueki, Jun Kikuchi, Kohsuke Ohmatsu, Masahiro Terada, Takashi Ooi
    • Journal Title

      Asian J. Or. Chem

      Volume: 9 Issue: 4 Pages: 561-565

    • DOI

      10.1002/ajoc.202000067

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Direct allylic C-H alkylation of enol silyl ethers enabled by photoredox-Bronsted base hybrid catalysis2019

    • Author(s)
      Kohsuke Ohmatsu, Tsubasa Nakashima, Makoto Sato, and Takashi Ooi
    • Journal Title

      Nat. Commun.

      Volume: 10 Issue: 1 Pages: 2706-2706

    • DOI

      10.1038/s41467-019-10641-y

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Presentation] 概日リズムの長周期化を起こす新規分子の構造活性相関と標的同定2021

    • Author(s)
      森田 渉平・大松 亨介・廣田 毅・大井 貴史
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 光レドックス触媒とチオール触媒の協働作用によるシリルエノールエーテルのアリル位Mannich型反応2021

    • Author(s)
      中島 翼・大松 亨介・大井 貴史
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] シリルエノールエーテルのアリル位ヘテロアリール化反応2021

    • Author(s)
      藤森 春佳・大松 亨介・大井 貴史
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 水素原子移動触媒による含フッ素ベンジル位C-H官能基化反応2021

    • Author(s)
      藤田 博貴・大松 亨介・大井 貴史
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Zwitterionic 1,2,3-Triazolium Amidate as a Catalyst for Photoinduced Hydrogen-Atom Transfer Radical Alkylation2019

    • Author(s)
      Ryuhei Suzuki, Kohsuke Ohmatsu, Takashi Ooi
    • Organizer
      第12回有機触媒シンポジウム
    • Related Report
      2019 Annual Research Report
  • [Presentation] Zwitterionic 1,2,3-Triazolium Amidate as a Catalyst for Photoinduced Hydrogen-Atom Transfer Radical Alkylation2019

    • Author(s)
      Ryuhei Suzuki, Kohsuke Ohmatsu, Takashi Ooi
    • Organizer
      2019 International C-H Functionalization Workshop
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Zwitterionic 1,2,3-Triazolium Amidate as a Catalyst for Photoinduced Hydrogen-Atom Transfer Radical Alkylation2019

    • Author(s)
      Ryuhei Suzuki, Kohsuke Ohmatsu, Takashi Ooi
    • Organizer
      The 1st International Symposium on Hybrid Catalysis for Enabling Molecular Synthesis on Demand
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Direct Allylic C-H Alkylation of Enol Silyl Ethers Enabled by Photoredox-Br?nsted Base Hybrid Catalysis2019

    • Author(s)
      Nakashima, T.; Ohmatsu, K.; Ooi, T.
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Hybrid Catalysis for Catalytic Stereoconversion of L-Amino Acid Derivatives to D-Isomers2019

    • Author(s)
      Nagato, Y.; Ohmatsu, K.; Ooi,T.
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] ラジカルカチオンの強酸性の活用にもとづくケテンシリルアセタールのアリル位アルキル化反応2019

    • Author(s)
      孫福凌、大松亨介、大井貴史
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] パラジウム-ハロゲン化物イオン協働触媒作用によるカルボニル化合物のアリル化反応2019

    • Author(s)
      松山菜歩、大松亨介、大井貴史
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 光レドックス触媒とブレンステッド塩基触媒の協働作用によるシリルエノールエーテルのアリル位C-Hアルキル化反応2019

    • Author(s)
      第11回有機触媒シンポジウム
    • Organizer
      中島翼、佐藤真、大松亨介、大井貴史
    • Related Report
      2018 Annual Research Report
  • [Presentation] 光レドックス触媒とブレンステッド塩基触媒の協働作用によるシリルエノールエーテルのアリル位C-Hアルキル化反応2019

    • Author(s)
      中島翼、佐藤真、大松亨介、大井貴史
    • Organizer
      第49回中部化学関係学協会支部連合秋季大会
    • Related Report
      2018 Annual Research Report
  • [Presentation] α-アミノカルボニル化合物の触媒的異性化反応2019

    • Author(s)
      永戸雄也、大松亨介、大井貴史
    • Organizer
      第49回中部化学関係学協会支部連合秋季大会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 1,2,3-トリアゾールを鍵骨格とする超分子キラル酸触媒の開発2019

    • Author(s)
      鈴木隆平 、大松亨介、大井貴史
    • Organizer
      第35回有機合成化学セミナー
    • Related Report
      2018 Annual Research Report
  • [Presentation] アニオン捕捉型超分子キラルブレンステッド酸触媒の開発と応用2019

    • Author(s)
      鈴木隆平, 大松亨介, 大井貴史
    • Organizer
      第113回有機合成シンポジウム
    • Related Report
      2018 Annual Research Report

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Published: 2018-04-23   Modified: 2022-01-27  

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