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Creation of heterobimetallic complexes utilizing hybrid-type NHC ligand for development of cooperative reaction site

Research Project

Project/Area Number 17K05805
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Inorganic chemistry
Research InstitutionYokohama National University

Principal Investigator

Yamaguchi Yoshitaka  横浜国立大学, 大学院工学研究院, 教授 (80313477)

Co-Investigator(Kenkyū-buntansha) 橋本 徹  横浜国立大学, 大学院工学研究院, 助教 (90710898)
Project Period (FY) 2017-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2018: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2017: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Keywords金属錯体触媒 / ニッケル錯体 / モノアニオン性3座ピンサー型配位子 / 不活性結合活性化 / クロスカップリング反応 / ヒドロホウ素化反応 / 鉄塩錯体 / 3座ピンサー型錯体 / モノアニオン性3座配位子 / 炭素-酸素結合切断 / 炭素-炭素結合生成 / 炭素-炭素結合生成反応 / ホウ素化反応 / 第一列後周期遷移金属元素 / NHC-ホウ素錯体 / 炭素-酸素結合切断 / 炭素-炭素結合生成反応 / 金属錯体 / 含窒素環状カルベン / 異種複核錯体
Outline of Final Research Achievements

Systematic synthesis of nickel complexes bearing a monoanionic tridentate pincer-type ligand and the catalytic ability of these complexes were investigated. Cross-coupling reactions using aryl Grignard reagents as nucleophiles were examined. In cases of aryl chlorides and -fluorides as electrophiles, the O,N,P- and N,N,P-pincer-type nickel complexes acted as effective catalysts for the coupling reaction. Using allylic ethers, the relatively robust C-O bond cleavage occurred to afford corresponding allylbenzene derivatives in good to excellent yields. Furthermore, the O,N,P-nickel complex acted as an effective catalyst for the highly Markovnikov-selective hydroboration of vinylarenes using bis(pinacolate)diboron.
Bis(triphenylphosphoranylidene)ammonium tetrachloroferrate, (PPN)[FeCl4], exhibited high stability toward air and moisture and acted as an effective catalyst for the cross-coupling reaction of secondary alkyl bromides with aryl Grignard reagents.

Academic Significance and Societal Importance of the Research Achievements

有機化合物の特定の結合切断を伴う新たな結合生成反応や炭素-炭素二重結合などの不飽和結合に対する有機基質の選択的な付加反応を実現する金属錯体触媒の開発は新たな有機合成の方法論を構築するうえで重要な課題である。さらに,金属錯体に主眼を置いた触媒開発研究は錯体化学のみならず有機合成化学において重要は情報を提供できる。金属錯体触媒を用いた新たな方法論の開発は,省エネルギープロセスの開発に寄与するだけでなく,持続可能な物質社会を永続的に発展させるための重要な課題である。本研究で開発したニッケル錯体はこれらの基礎研究に資するものであり,関連分野への波及効果が期待できる。

Report

(4 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • 2017 Research-status Report
  • Research Products

    (31 results)

All 2020 2019 2018 2017 Other

All Journal Article (7 results) (of which Peer Reviewed: 7 results,  Open Access: 1 results) Presentation (22 results) (of which Int'l Joint Research: 5 results,  Invited: 1 results) Remarks (1 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Cross‐Coupling Reactions of Alkyl Halides with Aryl Grignard Reagents Using a Tetrachloroferrate with an Innocent Countercation2019

    • Author(s)
      Hashimoto Toru、Maruyama Tsubasa、Yamaguchi Takamichi、Matsubara Yutaka、Yamaguchi Yoshitaka
    • Journal Title

      Advanced Synthesis & Catalysis

      Volume: 361 Issue: 18 Pages: 4232-4236

    • DOI

      10.1002/adsc.201900568

    • NAID

      120006714782

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cross-Coupling Reaction of Allylic Ethers with Aryl Grignard Reagents Catalyzed by a Nickel Pincer Complex2019

    • Author(s)
      Hashimoto Toru、Funatsu Kei、Ohtani Atsufumi、Asano Erika、Yamaguchi Yoshitaka
    • Journal Title

      Molecules

      Volume: 24 Issue: 12 Pages: 2296-2296

    • DOI

      10.3390/molecules24122296

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] β-diketiminato-based pincer-type nickel(II) complex: Synthesis and catalytic performance in the cross-coupling reaction of aryl fluorides with aryl Grignard reagents2019

    • Author(s)
      Nobutaka Kurisu, Erika Asano, Yuki Hatayama, Youji Kurihara, Toru Hashimoto, Kei Funatsu, Kazuyoshi Ueda, Yoshitaka Yamaguchi
    • Journal Title

      European Journal of Inorganic Chemistry

      Volume: - Issue: 1 Pages: 126-133

    • DOI

      10.1002/ejic.201801179

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Acetylacetonato-based pincer-type nickel(II) complexes: Synthesis and catalysis in cross-couplings of aryl chlorides with arylmagnesium bromides2018

    • Author(s)
      Erika Asano, Yuki Hatayama, Nobutaka Kurisu, Youji Kurihara, Shinji Ishihara, Toru Hashimoto, Kazuyoshi Ueda, Hirotaka Nagao, Yoshitaka Yamaguchi
    • Journal Title

      Dalton Transactions

      Volume: 47 Issue: 24 Pages: 8003-8012

    • DOI

      10.1039/c8dt01295d

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis and reactivity of [M(η3-allyl)(η2-amidinato)(CO)2(phosphonium ylide)] (M = Mo, W): Investigation of the ligand properties of phosphonium ylides2018

    • Author(s)
      Takaki Daichi、Ogata Kenichi、Kurihara Youji、Ueda Kazuyoshi、Hashimoto Toru、Yamaguchi Yoshitaka
    • Journal Title

      Inorganica Chimica Acta

      Volume: 471 Pages: 310-315

    • DOI

      10.1016/j.ica.2017.11.019

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Iron(II) bipyridine complexes for the cross-coupling reaction of bromocyclohexane with phenylmagnesium bromide2017

    • Author(s)
      Matsubara Yutaka、Yamaguchi Takamichi、Hashimoto Toru、Yamaguchi Yoshitaka
    • Journal Title

      Polyhedron

      Volume: 128 Pages: 198-202

    • DOI

      10.1016/j.poly.2017.02.046

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of N-heterocyclic carbene boranes via silver N-heterocyclic carbene complexes2017

    • Author(s)
      Ono Shintaro、Watanabe Takashi、Nakamura Yosuke、Sato Hiroyasu、Hashimoto Toru、Yamaguchi Yoshitaka
    • Journal Title

      Polyhedron

      Volume: 137 Pages: 296-305

    • DOI

      10.1016/j.poly.2017.08.045

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Presentation] 三座ピンサー型ニッケル錯体を用いたビニルアレンのヒドロホウ素化反応2020

    • Author(s)
      塩田啓介,橋本徹,山口佳隆
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] PINCER-TYPE NICKEL(II) COMPLEXES: SYNTHESIS AND CATALYSIS IN THE CROSS-COUPLING OF ARYL FLUORIDES WITH ARYL GRIGNARD REAGENTS2019

    • Author(s)
      Nobutaka Kurisu, Erika Asano, Toru Hashimoto, Yoshitaka Yamaguchi
    • Organizer
      International Conference on Fluorine Chemistry 2019 Himeji
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 三座ピンサー型ニッケル錯体を用いたアリルエーテルとGrignard反応剤とのクロスカップリング反応2019

    • Author(s)
      船津啓,大谷充史,橋本徹,山口佳隆
    • Organizer
      第77 回有機合成化学協会関東支部シンポジウム
    • Related Report
      2019 Annual Research Report
  • [Presentation] Iron Salt-Catalyzed Cross-Coupling Reaction of Alkyl Halides with Aryl Grignard Reagents2019

    • Author(s)
      Toru Hashimoto, Tsubasa Maruyama, Masaru Matsugaki, Yoshitaka Yamaguchi
    • Organizer
      20th IUPAC International Symposium on Organometallic Chemistry Directed Towasrds Organic Synthesis
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Cross-Coupling of Organic Electrophiles with Aryl Grignard Reagents Catalyzed by Nickel(II) Pincer Complexes2019

    • Author(s)
      Toru Hashimoto, Kei Funatsu, Nobutaka Kurisu, Erika Asano, Yoshitaka Yamaguchi
    • Organizer
      International Congress on Pure & Applied Chemistry (ICPAC) Yangon 2019
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Hydroboration of Vinylarenes Catalyzed by Nickel Pincer Complexes2019

    • Author(s)
      Keisuke Shiota, Toru Hashimoto, Yoshitaka Yamaguchi
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 三座ピンサー型ニッケル錯体を用いたアリルエーテルと芳香族Grignard反応剤とのクロスカップリング反応2019

    • Author(s)
      船津啓,大谷充史,橋本徹,山口佳隆
    • Organizer
      第9回CSJ化学フェスタ2019
    • Related Report
      2019 Annual Research Report
  • [Presentation] 三座ピンサー型ニッケル錯体を用いたスチレン類のヒドロホウ素化反応2019

    • Author(s)
      塩田啓介,橋本徹,山口佳隆
    • Organizer
      第9回CSJ化学フェスタ2019
    • Related Report
      2019 Annual Research Report
  • [Presentation] 3座ピンサー型鉄およびニッケル錯体の合成と触媒反応2019

    • Author(s)
      山口佳隆
    • Organizer
      第29回神奈川大学平塚シンポジウム
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] オニウムイオンを対カチオンに有する鉄塩錯体を用いたクロスカップリング反応2018

    • Author(s)
      丸山翼、橋本徹、山口佳隆
    • Organizer
      第75回有機合成化学協会関東支部シンポジウム
    • Related Report
      2018 Research-status Report
  • [Presentation] 鉄塩錯体を用いたハロゲン化アルキルと芳香族Grignard反応剤とのクロスカップリング反応2018

    • Author(s)
      丸山翼,松垣智,橋本徹,山口佳隆
    • Organizer
      日本プロセス化学会2018サマーシンポジウム
    • Related Report
      2018 Research-status Report
  • [Presentation] Cross-Coupling of Allylic Ethers with Grignard Reagents Using Nickel Pincer Complexes2018

    • Author(s)
      Toru Hashimoto, Atsufumi Ohtani, Kei Funatsu, Yoshitaka Yamaguchi
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] Cross-Coupling of Alkyl Halides with Aryl Grignard Reagents Catalyzed by Tetrahalogenoferrate Salt2018

    • Author(s)
      Toru Hashimoto, Tsubasa Maruyama, Masaru Matsugaki, Yoshitaka Yamaguchi
    • Organizer
      The 14th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-14)
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] ホスホニウムを対カチオンに有する鉄塩錯体を用いたハロゲン化アルキルと芳香族Grignard反応剤とのクロスカップリング反応2018

    • Author(s)
      松垣智、丸山翼、橋本徹、山口佳隆
    • Organizer
      第76 回有機合成化学協会関東支部シンポジウム
    • Related Report
      2018 Research-status Report
  • [Presentation] Cross-Coupling of Alkyl Halides with Aryl Grignard Reagents using Ferrate Salts2018

    • Author(s)
      Toru Hashimoto, Tsubasa Maruyama, Yoshitaka Yamaguchi
    • Organizer
      IRCCS-JST CREST Joint Symposium
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Cross-Coupling of Alkyl Halides with Aryl Grignard Reagents using Ferrate Salts2018

    • Author(s)
      Tsubasa Maruyama, Toru Hashimoto, Yoshitaka Yamaguchi
    • Organizer
      日本化学会 第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 三座ピンサー型ニッケル錯体を用いた塩化アリールとアリールGrignard反応剤のクロスカップリング反応2017

    • Author(s)
      橋本徹、浅野瑛里香、栗栖伸隆、山口佳隆
    • Organizer
      第73回有機合成化学協会関東支部シンポジウム(目白シンポジウム)
    • Related Report
      2017 Research-status Report
  • [Presentation] ニッケルピンサー型錯体を用いた芳香族塩化物と芳香族Grignard反応剤とのクロスカップリング反応2017

    • Author(s)
      橋本徹, 浅野瑛里香, 栗栖伸隆, 山口佳隆
    • Organizer
      第6回JACI/GSCシンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] Biaryl Coupling Reaction of Haloarenes with Grignard Reagents Using Nickel Pincer Complexes2017

    • Author(s)
      Toru Hashimoto, Erika Asano, Nobutaka Kurisu, and Yoshitaka Yamaguchi
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] Coupling of Alkyl Halides with Grignard Reagents Using Tetrahalogenoferrate Salts2017

    • Author(s)
      Tsubasa Maruyama, Toru Hashimoto, and Yoshitaka Yamaguchi
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 鉄塩錯体の合成とクロスカップリング反応への応用2017

    • Author(s)
      丸山翼・橋本徹・山口佳隆
    • Organizer
      第7回CSJ化学フェスタ2017
    • Related Report
      2017 Research-status Report
  • [Presentation] イオン対型鉄塩錯体の合成とハロゲン化アルキルを用いた熊田・玉尾・Corriu カップリング反応2017

    • Author(s)
      丸山翼、橋本徹、山口佳隆
    • Organizer
      第74回有機合成化学協会関東支部シンポジウム(新潟シンポジウム)
    • Related Report
      2017 Research-status Report
  • [Remarks] 研究者総覧

    • URL

      https://er-web.ynu.ac.jp/html/YAMAGUCHI_Yoshitaka/ja.html

    • Related Report
      2019 Annual Research Report
  • [Patent(Industrial Property Rights)] クロスカップリング体の製造方法及びテトラハロゲノ鉄塩2017

    • Inventor(s)
      山口佳隆,橋本徹
    • Industrial Property Rights Holder
      山口佳隆,橋本徹
    • Industrial Property Rights Type
      特許
    • Filing Date
      2017
    • Related Report
      2017 Research-status Report

URL: 

Published: 2017-04-28   Modified: 2021-02-19  

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