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Development of highly active metal catalysts based on bicyclic NHC ligands

Research Project

Project/Area Number 15K18832
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Chemical pharmacy
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) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2017: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2016: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywords遷移金属触媒 / 含窒素複素環式カルベン / 銅 / ニッケル / カップリング反応 / NHC配位子 / 銅触媒 / ニッケル触媒 / N-ヘテロ環状カルベン / 配位子
Outline of Final Research Achievements

NHC ligands are generally equipped with bulky N-substituents, while our bicyclic NHC possess a bulky phenyl ring on the non-carbenic carbons. In this study, we applied our novel NHC ligands to transitional metal catalysts and investigated the effects of the unique steric properties.
The copper complexes supported by our NHCs were stable on a bench and successfully catalyzed the borylation of arylbromide. In this catalysis, the bicyclic NHC ligand showed significantly higher reactivity toward hindered substrates than ubiquitous NHCs, which indicates that the bicyclic NHC is bulky but accessible. On the nickel catalysis, our ligand effectively worked for the Kumada-Tamao-Corriu coupling of arylboromides with tertiary alkyl Grignard reagents. We also developed the stable NHC-Ni precatalyst which finely worked for Suzuki-Miyaura cross-coupling.

Report

(4 results)
  • 2017 Annual Research Report   Final Research Report ( PDF )
  • 2016 Research-status Report
  • 2015 Research-status Report
  • Research Products

    (11 results)

All 2017 2016 2015

All Journal Article (5 results) (of which Peer Reviewed: 5 results,  Acknowledgement Compliant: 3 results) Presentation (6 results)

  • [Journal Article] A Study of the Strength of a Template Molecule—A Functional Monomer Interaction That Affects the Performance of Molecularly Imprinted Polymers and Its Application to Chiral Amplification2017

    • Author(s)
      Takuro Yasuyama, Hirofumi Matsunaga, Shin Ando, and Tadao Ishizuka
    • Journal Title

      Chemical and Pharmaceutical Bulletin

      Volume: 65 Issue: 4 Pages: 396-402

    • DOI

      10.1248/cpb.c16-00974

    • NAID

      130005529661

    • ISSN
      0009-2363, 1347-5223
    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A dramatic synergistic effect of a flexible achiral linker on a rigid chiral cis-1,2-diamine bifunctional organocatalyst2017

    • Author(s)
      Hirofumi Matsunaga, Daisuke Tajima, Tetsuro Kawauchi, Takuro Yasuyama, Shin Ando and Tadao Ishizuka
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 15 Issue: 14 Pages: 2892-2896

    • DOI

      10.1039/c6ob02743a

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] An N-Heterocyclic Carbene-Nickel Half-Sandwich Complex as a Precatalyst for Suzuki-Miyaura Coupling of Aryl/Heteroaryl Halides with Aryl/Heteroarylboronic Acids2017

    • Author(s)
      Shin Ando, Hirofumi Matsunaga, Tadao Ishizuka
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 82 Issue: 2 Pages: 1266-1272

    • DOI

      10.1021/acs.joc.6b02666

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] An N-heterocyclic carbene-based nickel catalyst for the Kumada-Tamao-Corriu coupling of aryl bromides and tertiary alkyl Grignard reagents2016

    • Author(s)
      Shin Ando, Mai Mawatari, Hirofumi Matsunaga, Tadao Ishizuka
    • Journal Title

      Tetrahedron Letters

      Volume: 57 Issue: 30 Pages: 3287-3290

    • DOI

      10.1016/j.tetlet.2016.06.042

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] A Bicyclic N-Heterocyclic Carbene as a Bulky but Accessible Ligand: Application to the Copper-Catalyzed Borylations of Aryl Halides2015

    • Author(s)
      Shin Ando, Hirofumi Matsunaga, Tadao Ishizuka
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 80 Issue: 19 Pages: 9671-9681

    • DOI

      10.1021/acs.joc.5b01721

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] NHC-Cu錯体の触媒するアリールブロマイドのホウ素化反応2017

    • Author(s)
      安藤 眞、松永 浩文、石塚 忠男
    • Organizer
      日本薬学会第137年会
    • Place of Presentation
      東北大学川内地区
    • Year and Date
      2017-03-24
    • Related Report
      2016 Research-status Report
  • [Presentation] 新規NHC-ニッケル触媒の開発とカップリング反応への応用2017

    • Author(s)
      安藤 眞、馬渡 麻衣、松永 浩文、石塚 忠男
    • Organizer
      第111回有機合成シンポジウム
    • Related Report
      2017 Annual Research Report
  • [Presentation] ビシクロ[2.2.1]ヘプタン骨格を持つ新規ビシクロNHC配位子の合成と物性の検討2017

    • Author(s)
      宮田 綾太、安藤 眞、松永 浩文、石塚 忠男
    • Organizer
      第34回日本薬学会九州支部大会
    • Related Report
      2017 Annual Research Report
  • [Presentation] DHASI-Ni錯体の触媒するブロモアレーンと第三級アルキルGrignard試薬のカップリング反応2016

    • Author(s)
      安藤 眞、馬渡 麻衣、松永 浩文、石塚 忠男
    • Organizer
      日本薬学会第136年会
    • Place of Presentation
      パシフィコ横浜
    • Year and Date
      2016-03-26
    • Related Report
      2015 Research-status Report
  • [Presentation] DHASICy-ニッケル錯体を用いた芳香環への三級炭素の導入2015

    • Author(s)
      馬渡 麻衣、安藤 眞、松永 浩文、石塚 忠男
    • Organizer
      第32回日本薬学会九州支部大会
    • Place of Presentation
      九州保健福祉大学
    • Year and Date
      2015-11-28
    • Related Report
      2015 Research-status Report
  • [Presentation] メソ型分子骨格の非対称化に基づく不斉NHC配位子の開発2015

    • Author(s)
      安藤 眞、松永 浩文、石塚 忠男
    • Organizer
      シンポジウム モレキュラーキラリティー
    • Place of Presentation
      早稲田大学 西早稲田キャンパス
    • Year and Date
      2015-06-12
    • Related Report
      2015 Research-status Report

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Published: 2015-04-16   Modified: 2019-03-29  

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