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Synthesis and evaluation of properties of imidazo[1,5-a]pyridine carbenes

Research Project

Project/Area Number 16K05769
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionGifu University

Principal Investigator

Shibahara Fumitoshi  岐阜大学, 工学部, 准教授 (60362175)

Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2018: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2017: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2016: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywords含窒素複素環カルベン / 遷移金属触媒 / 配位子 / カルベン / 複素環 / 有機化学
Outline of Final Research Achievements

Previously, we estimated that imidazo[1,5-a]pyridine derived carbenes have different electronic character from the conventional carbenes, thus those compounds were actually synthesized and evaluated those properties. The synthesis were carried out with our previously developed methods and a variety of compounds were obtained. The compounds readily derived to the corresponding Rh-CO complexes, and we measured several spectra of the complexes and estimated their donor and accepter characters by DFT calculations. As a result, we revealed that the carbenes indicated meaningful pi-accepting character. With this feature, we also assayed catalytic activities for several reactions and found that the catalyst having the ligands showed good catalytic activity when the reaction includes migratory insertion, and beta-elimination that usually well induced by pi-acidic metals.

Academic Significance and Societal Importance of the Research Achievements

これまで含窒素複素環カルベンは、アクセプター性はほとんど無いとされていて、実際にそれの性質を利用した錯体触媒開発が進められてきた。しかし、アクセプター性を持つ同様の化学種の提供は、新しい触媒活性を持つ化学種を創出することにつながり、新しい触媒反応を展開することが可能になる。今回われわれは、実際にそのような性質を持つ含窒素カルベンの創出に成功し、それらが確かに、これまで使われてきた含窒素複素環カルベン配位子を持つ金属錯体とは異なる反応性を示すことを証明したため、今後、その性質を利用した新たな触媒反応開発の展開が見込まれる。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (14 results)

All 2018 2017 2016

All Journal Article (5 results) (of which Peer Reviewed: 5 results,  Acknowledgement Compliant: 2 results) Presentation (9 results) (of which Int'l Joint Research: 4 results,  Invited: 1 results)

  • [Journal Article] Synthesis of Chiral Selenazolines from N-Acyloxazolidinones via a Selenative Rearrangement of Chiral Cyclic Skeletons2018

    • Author(s)
      Shibahara Fumitoshi、Fukunaga Tomoki、Kubota Saki、Yoshida Akihito、Murai Toshiaki
    • Journal Title

      Organic Letters

      Volume: 20 Issue: 18 Pages: 5826-5830

    • DOI

      10.1021/acs.orglett.8b02520

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Chelation-assisted β-selective direct C-H bond arylation of 2-thienylthioamide catalyzed by Pd-1,10-phenanthroline complexes2018

    • Author(s)
      Shibahara Fumitoshi、Asai Yusuke、Murai Toshiaki
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 印刷中 Issue: 7 Pages: 1323-1326

    • DOI

      10.1002/ajoc.201800160

    • Related Report
      2018 Annual Research Report 2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Selenolactams as Synthetic Intermediates for the Synthesis of Polycyclic Amines via Seleno-Claisen Rearrangements2018

    • Author(s)
      Shibahara Fumitoshi、Suzuki Masafumi、Kubota Saki、Fukunaga Tomoki、Udagawa Taro、Murai Toshiaki
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 83 Issue: 6 Pages: 3078-3089

    • DOI

      10.1021/acs.joc.8b00306

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Imidazo[1,5-a]pyridin-3-ylidenes as π-accepting carbene ligands: substituent effects on properties of N-heterocyclic carbenes2017

    • Author(s)
      河戸勇磨、芝原文利、村井利昭
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 15 Issue: 8 Pages: 1810-1820

    • DOI

      10.1039/c6ob02827f

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] 1-Substituted-imidazo[1,5-a]pyridin-3-ylidenes as Highly Efficient Ligands for Rh- and Ir-catalyzed Transfer Hydrogenation of Carbonyl Compounds2016

    • Author(s)
      河戸勇磨、芝原文利、村井利昭
    • Journal Title

      Chemistry Letters

      Volume: 45 Issue: 11 Pages: 1327-1329

    • DOI

      10.1246/cl.160740

    • NAID

      130005509483

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Direct C-H Bond Arylation of Thienylthioamides Catalyzed by Pd-1,10-phenanthroline Complexes2018

    • Author(s)
      芝原文利
    • Organizer
      Τhe 14th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-14)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Direct C-H Bond Arylation of Thienylthioamides by Pd/phenanthroline Complexes2018

    • Author(s)
      芝原文利
    • Organizer
      The 4th International Symposium on C-H Activation (ISCHA4)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Several Transition Metal Complexes of Imidazo[1,5-a]Pyridine Carbenes and their Catalytic Applications2018

    • Author(s)
      芝原文利
    • Organizer
      XXVIII International Conference on Organometallic Chemistry (ICOMC2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Pd/Phen-catalyzed Direct C-H Bond Arylation of Thienylthioamides2018

    • Author(s)
      芝原文利
    • Organizer
      3rd International Symposium on Precisely Designed Catalysts with Customized Scaffolding
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 5-スルホニルイミダゾ[1,5‐a]ピリジンカルベンの合成2018

    • Author(s)
      金森真弥、服部鈴香、芝原文利、村井利昭
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] パラジウム触媒を用いるイミダゾ[1,5-a]ピリジンの逐次分子内直接 C-H アリール化-アルケニル化による高蛍光発光性化合物の開発2018

    • Author(s)
      花形 祥弥 、芝原 文利、村井 利昭
    • Organizer
      第65回 有機金属化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 1,5位および窒素上に嵩高い置換基を持つイミダゾ[1,5-a]ピリジンカルベンの合成2018

    • Author(s)
      柴田理古、芝原文利、村井利昭
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] セレノカルボニル化合物の性質を利用した合成反応の開発2018

    • Author(s)
      芝原文利、久保田早貴、鈴木雅史、福永知己、池山義基、村井利昭
    • Organizer
      第113回有機合成シンポジウム2018年【春】
    • Related Report
      2018 Annual Research Report
  • [Presentation] π酸性遷移金属-NHC 錯体:触媒反応への応用2017

    • Author(s)
      芝原 文利・河戸 勇磨・水野 貴大・村井 利昭
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Research-status Report

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Published: 2016-04-21   Modified: 2020-03-30  

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