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Development of Palladium-Catalyzed Stereoselective Enolate-Nucleophile Coupling Reactions

Research Project

Project/Area Number 19K15550
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionOsaka University (2021)
Hokkaido University (2019-2020)

Principal Investigator

Doi Ryohei  大阪大学, 工学研究科, 助教 (40780052)

Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2021: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2020: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2019: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywordsパラジウム触媒 / エノラート / 脱炭酸 / 炭素ー酸素結合切断 / 炭素ー炭素結合形成 / C-C結合形成 / C-O結合切断 / C-O結合活性化 / カップリング反応
Outline of Research at the Start

本研究課題では、遷移金属のひとつであるパラジウムを触媒として用いたエノラートと種々の求核剤のカップリング反応を開発する。エノラートは求核種であり、基本的には求電子剤との反応が一般的であるが、パラジウムを使うことで求核剤との反応が可能であることを立証する。エナンチオ選択的な反応(右手と左手の関係のモノを作り分ける)の開発を通して、創薬において重要なキラルビルディングブロックの創出を目指す。

Outline of Final Research Achievements

This research project aims to develop enantioselective carbon-carbon bond formation reactions based on catalytic palladium enolate formation. By combining a palladium catalyst with a biaryl type phosphine ligand, decarboxylative C-C coupling reactions involving C-O bond cleavage of hydroxyketone derivatives were successfully developed. In the alkynylation reaction, a ligand called XPhos gave the best yield. We have isolated and characterized a key palladium enolate intermediate by performing a stoichiometric reaction. The structure of the complex was confirmed by X-ray crystallography. The perfluoroarylation reaction was found to be applicable to installation of various polyfluoroarene derivatives. Cross-over experiments suggested that decarboxylation or reductive elimination was the rate-limiting step.

Academic Significance and Societal Importance of the Research Achievements

パラジウムエノラート種は従来、強塩基を用いて発生させたエノラートとパラジウム塩のトランスメタル化により調製することが一般的であった。本研究では、ヒドロキシケトンの炭素ー酸素結合のパラジウム錯体への酸化的付加が効率よく進行することを見出し、塩基を用いずともパラジウムエノラート種を発生させる手法について検討した。Buchwald配位子とよばれるビアリールホスフィンを用いることで、ケトンのアルキニル化およびパーフルオロアリール化が反応することを見出し、実際にケトンから塩基なしでパラジウムエノラートを生成できることを立証した。

Report

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

    (9 results)

All 2022 2021 2020 2019

All Journal Article (4 results) (of which Peer Reviewed: 4 results) Presentation (5 results) (of which Int'l Joint Research: 1 results)

  • [Journal Article] Palladium-Catalyzed Decarboxylative α-Polyfluoroarylation of Ketones2021

    • Author(s)
      Doi Ryohei、Hayashi Kanako、Sato Yoshihiro
    • Journal Title

      Chemistry Letters

      Volume: - Issue: 6 Pages: 1181-1183

    • DOI

      10.1246/cl.210092

    • NAID

      130008053407

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Nickel‐Catalyzed Acyl Group Transfer of o‐Alkynylphenol Esters Accompanied by C-O Bond Fission for Synthesis of Benzo[b]furan2021

    • Author(s)
      Doi Ryohei、Shimizu Koji、Ikemoto Yuma、Uchiyama Masashi、Koshiba Mikiko、Furukawa Atsushi、Maenaka Katsumi、Watanabe Satoshi、Sato Yoshihiro
    • Journal Title

      ChemCatChem

      Volume: 13 Issue: 8 Pages: 2086-2092

    • DOI

      10.1002/cctc.202001949

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Nickel Nanoparticle-catalyzed Carboxylation of Unsaturated Hydrocarbon with CO2 Using Sulfur-modified Au-supported Nickel Material2019

    • Author(s)
      Taniguchi Takahisa、Saito Nozomi、Doi Ryohei、Kimoto Arato、Hoshiya Naoyuki、Fujiki Katsumasa、Shuto Satoshi、Fujioka Hiromichi、Arisawa Mitsuhiro、Sato Yoshihiro
    • Journal Title

      Chemistry Letters

      Volume: 48 Issue: 11 Pages: 1406-1409

    • DOI

      10.1246/cl.190650

    • NAID

      130007741839

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Nickel-Catalyzed β-Carboxylation of Ynamides with Carbon Dioxide2019

    • Author(s)
      Doi Ryohei、Okano Taichi、Abdullah Iman、Sato Yoshihiro
    • Journal Title

      Synlett

      Volume: 30 Issue: 09 Pages: 1048-1052

    • DOI

      10.1055/s-0037-1611529

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] Ni(0)錯体によるジフルオロシリルエノールエーテルの位置選択的なC(sp2)-F結合切断反応2022

    • Author(s)
      梶原光稀、土井良平、生越専介
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Ni-Catalyzed Synthesis of Benzofurans via C-O Bond Activation of Esters2020

    • Author(s)
      Ryohei Doi, Koji Shimizu, Yuma Ikemoto, Mikiko Koshiba, Masashi Uchiyama, Satoshi Watanabe, Yoshihiro Sato
    • Organizer
      第18回 次世代を担う有機化学シンポジウム 口頭発表(英語)2L-01
    • Related Report
      2020 Research-status Report
  • [Presentation] Pd触媒によるC-O結合切断をカギとしたアシルオキシケトンのα位アルキニル化反応2019

    • Author(s)
      藪田明優、土井良平、佐藤 美洋
    • Organizer
      第9回CSJ化学フェスタ
    • Related Report
      2019 Research-status Report
  • [Presentation] Palladium-Catalyzed Decarboxylative Alkynylation of Ketones2019

    • Author(s)
      Ryohei Doi, Akimasa Yabuta, Yoshihiro Sato
    • Organizer
      The 14th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-14)
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Pd触媒を用いたC(sp3)-O結合切断を鍵としたα-アルキニルケトンの合成2019

    • Author(s)
      藪田明優、土井良平、佐藤 美洋
    • Organizer
      第17回次世代を担う有機化学シンポジウム
    • Related Report
      2019 Research-status Report

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Published: 2019-04-18   Modified: 2023-01-30  

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