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Development of novel NHO ligands for transition-metal catalysts

Research Project

Project/Area Number 21K06456
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 47010:Pharmaceutical chemistry and drug development sciences-related
Research InstitutionKumamoto University

Principal Investigator

Ando Shin  熊本大学, 大学院生命科学研究部(薬), 助教 (00622599)

Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2023: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2022: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2021: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Keywords配位子 / 炭素 / 遷移金属触媒
Outline of Research at the Start

この研究は有機化学反応を円滑に進めるために有用な触媒、中でも金属を含んだ金属触媒の開発を目指します。溶液に溶けて機能する金属触媒を開発する際には金属に様々な機能を付与する配位子という存在が重要で、この研究ではこの配位子として奇妙で魅力的な性質を持つ有機化合物を用います。NHOと呼ばれるこの化合物は触媒への応用例がほとんど無く、世界に先駆けて広く有用なNHO含有金属触媒の開発を検討します。

Outline of Final Research Achievements

N-heterocyclic olefin (NHO) ligands are alkylidene derivatives of NHCs that have emerged as highly electron-donative ligands over the past decade. Despite of their intriguing binding abilities of NHO ligands, reports of NHO-metal complexes remain limited. In this study, we synthesized a novel NHO that was equipped with a bicyclic framework. This 2-methyleneimidazolidine-based NHO was successfully applied to syntheses of Rh and Pd complexes, and the structures of the isolated complexes were confirmed via XRD and computational studies. Additionally, we found that [(NHO)PdCl2]2 complexes had a phosphine co-ligand that proved effective as a catalyst for Suzuki-Miyaura coupling at ambient temperature. By optimizing the N-substituents of NHO ligands and a phosphine co-ligand, we developed a [(NHO)Pd{[2-(CH3O)C6H4]3P}Cl2] complex as a catalyst that shows good catalytic activity.

Academic Significance and Societal Importance of the Research Achievements

望む化学変換に有効な金属触媒系を確立するには、配位子の電子供与性の調節が不可欠であり、その多様性の拡張は実現可能な化学反応の多様化につながる。本研究では、電子供与性が高いことが知られているものの、錯体合成等への応用が極限定的なNHOを基盤構造として用いた。独自に飽和型NHOを開発して種々検討した結果、その電子供与性は汎用されるNHC配位子よりも高く、既知の不飽和型NHOよりも低い、NHCと不飽和NHOの間の性質を示す配位子であることが分かった。独自にNHO-Pd錯体が触媒として機能する例も見出したことから、更なる検討によって新奇反応を実現し得る金属触媒の開発につながるものと期待する。

Report

(4 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Research-status Report
  • 2021 Research-status Report
  • Research Products

    (13 results)

All 2023 2022 2021

All Journal Article (7 results) (of which Peer Reviewed: 7 results) Presentation (6 results)

  • [Journal Article] Syntheses of Aryl Thioethers <i>via</i> Aromatic Substitution of Aryl Halides at 0 to 25 °C2023

    • Author(s)
      Tsuzaki Marina、Ando Shin、Ishizuka Tadao
    • Journal Title

      Chemical and Pharmaceutical Bulletin

      Volume: 71 Issue: 7 Pages: 620-623

    • DOI

      10.1248/cpb.c23-00232

    • ISSN
      0009-2363, 1347-5223
    • Year and Date
      2023-07-01
    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of a N‐heterocyclic Olefin‐Ligated Pd Complex [(NHO)Pd{[2‐(CH3O)C6H4]3P}Cl2] as a Catalyst for Suzuki-Miyaura Coupling2023

    • Author(s)
      Ando Shin、Tanaka Ayako、Ishizuka Tadao
    • Journal Title

      European Journal of Organic Chemistry

      Volume: 26

    • DOI

      10.1002/ejoc.202300801

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] N-heterocyclic carbene ligands with a bicyclic framework fused with either naphthalene or anthracene2023

    • Author(s)
      Ando Shin、Kono Yoko、Ishizuka Tadao
    • Journal Title

      Journal of Organometallic Chemistry

      Volume: 984 Pages: 122576-122576

    • DOI

      10.1016/j.jorganchem.2022.122576

    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] Bisamidate-functionalized NHC ligands: Electronic and steric influences of N-substituents on the bisamidate moieties2022

    • Author(s)
      Hirota Yurina、Ando Shin、Ishizuka Tadao
    • Journal Title

      Tetrahedron

      Volume: 108 Pages: 132668-132668

    • DOI

      10.1016/j.tet.2022.132668

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Etherification via Aromatic Substitution on 1,3-Disubstituted Benzene Derivatives2022

    • Author(s)
      Tsuzaki Marina、Ando Shin、Ishizuka Tadao
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 87 Issue: 2 Pages: 1357-1365

    • DOI

      10.1021/acs.joc.1c02670

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Imidazolinium Salts by Pd/C‐Catalyzed Dehydrogenation of Imidazolidines2021

    • Author(s)
      Ando Shin、Xiao Bowen、Ishizuka Tadao
    • Journal Title

      European Journal of Organic Chemistry

      Volume: 2021 Issue: 32 Pages: 4551-4554

    • DOI

      10.1002/ejoc.202100914

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Rhodium and Palladium Complexes of NHeterocyclic Olefin (NHO) Ligand Fused with the 9,10-Dihydro-9,10-ethanoanthracene Framework2021

    • Author(s)
      Shin Ando, Akio Ohara, Tomohiko Ohwada, Tadao Ishizuka
    • Journal Title

      Organometallics

      Volume: 40 Issue: 21 Pages: 3668-3677

    • DOI

      10.1021/acs.organomet.1c00503

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Presentation] 極めて温和な条件下での芳香族置換反応による芳香族エーテル類合成研究2022

    • Author(s)
      津崎まりな, 安藤眞, 石塚忠男
    • Organizer
      第120回有機合成シンポジウム
    • Related Report
      2022 Research-status Report
  • [Presentation] 極めて温和な条件下で進行する芳香環上での求核的ハロゲン置換反応の開発2021

    • Author(s)
      津崎 まりな、安藤 眞、石塚 忠男
    • Organizer
      第58回化学関連支部合同九州大会
    • Related Report
      2021 Research-status Report
  • [Presentation] 極めて温和な条件下で進行する芳香環上での求核的ハロゲン置換反応の開発2021

    • Author(s)
      津崎 まりな、安藤 眞、石塚 忠男
    • Organizer
      第118回有機合成シンポジウム
    • Related Report
      2021 Research-status Report
  • [Presentation] 極めて温和な条件下で進行する芳香環上での求核的ハロゲン置換反応の開発2021

    • Author(s)
      津崎 まりな、安藤 眞、石塚 忠男
    • Organizer
      第47回反応と合成の進歩シンポジウム
    • Related Report
      2021 Research-status Report
  • [Presentation] 極めて温和な条件下で進行する芳香環上での求核的ハロゲン置換反応の基質適用範囲拡大に向けた検討2021

    • Author(s)
      津崎 まりな、安藤 眞、石塚 忠男
    • Organizer
      第38回日本薬学会九州山口支部大会
    • Related Report
      2021 Research-status Report
  • [Presentation] ビシクロ環を備えたNHC配位子の立体的・電子的性質の解析2021

    • Author(s)
      大塚 澪、安藤 眞、石塚 忠男
    • Organizer
      第38回日本薬学会九州山口支部大会
    • Related Report
      2021 Research-status Report

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Published: 2021-04-28   Modified: 2025-01-30  

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