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Exploration of Catalytic Generation of Carbene through Two-Fold Cleavage of Inert Bonds

Research Project

Project/Area Number 17K19122
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Research Field Organic chemistry and related fields
Research InstitutionInstitute of Physical and Chemical Research (2019)
Okayama University (2017-2018)

Principal Investigator

Asako Sobi  国立研究開発法人理化学研究所, 環境資源科学研究センター, 上級研究員 (80737289)

Project Period (FY) 2017-06-30 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥6,110,000 (Direct Cost: ¥4,700,000、Indirect Cost: ¥1,410,000)
Fiscal Year 2018: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Fiscal Year 2017: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
Keywordsモリブデン / タングステン / カルボニル化合物 / シクロプロパン / 脱酸素 / カルベン / 炭素-水素結合活性化 / 炭素-炭素結合活性化 / 炭素-水素結合切断 / 炭素-炭素結合切断 / ルテニウム / 不活性結合切断
Outline of Final Research Achievements

Novel chemical transformations based on the generation of metal carbenes through two-fold cleavage of the inert bonds in stable compounds have been explored. Mo/quinone was found to efficiently catalyze a series of intramolecular and intermolecular reactions with the cleavage of C=O double bond of carbonyl compounds and the successive cleavage of gem C-C single bonds of cyclopropanes. DFT studies have revealed the nature of the bond cleavage steps as well as the reactivities of the metal carbenes.

Academic Significance and Societal Importance of the Research Achievements

近年、不活性な極性および無極性単結合の切断を鍵とする触媒的精密有機合成反応がさかんに研究されており、従来は不可能であった物質変換を可能にすることで、合成ルートの効率化、省エネルギー化、コスト削減に貢献している。しかしながら、不活性結合二重切断によるカルベン生成反応はほぼ手つかずの未開拓分野であった。有機合成化学の多様性、有用性を著しく向上させた不活性単結合切断化学の歴史に倣い、今現在「不活性」と考えられている結合二重切断化学を新たに展開することができれば、これまでに確立された合成戦略を大きく変えるような画期的な新展開をもたらすことができる。

Report

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

    (12 results)

All 2020 2019 2018 2017 Other

All Journal Article (2 results) (of which Peer Reviewed: 2 results,  Open Access: 2 results) Presentation (7 results) (of which Int'l Joint Research: 2 results,  Invited: 1 results) Remarks (3 results)

  • [Journal Article] Deoxygenative Insertion of Carbonyl Carbon into a C(sp3)-H Bond: Synthesis of Indolines and Indoles2019

    • Author(s)
      Asako Sobi、Ishihara Seina、Hirata Keiya、Takai Kazuhiko
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Issue: 25 Pages: 9832-9836

    • DOI

      10.1021/jacs.9b05428

    • NAID

      120006859680

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Use of Cyclopropane as C1 Synthetic Unit by Directed Retro-Cyclopropanation with Ethylene Release2018

    • Author(s)
      Sobi Asako, Takaaki Kobashi, Kazuhiko Takai
    • Journal Title

      Journal of the American Chemical Society

      Volume: 140 Issue: 45 Pages: 15425-15429

    • DOI

      10.1021/jacs.8b09297

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access
  • [Presentation] Exploration of Organic Synthesis Using Abundant and Stable Compounds2020

    • Author(s)
      Sobi Asako
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Directed Retro-Cyclopropanation with Metal-Quinone Complexes2019

    • Author(s)
      Sobi Asako, Takaaki Kobashi, Kazuhiko Takai
    • Organizer
      the 23rd International Symposium on Olefin Metathesis and Related Chemistry (ISOM XXIII)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Retro-Cyclopropanation with Metal-Quinone Complexes2019

    • Author(s)
      Sobi Asako, Takaaki Kobashi, Kazuhiko Takai
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Deoxygenative Cyclization of Carbonyl Compounds Catalyzed by Molybdenum/Quinone Complexes2018

    • Author(s)
      Sobi Asako, Seina Ishihara, Keiya Hirata, Kazuhiko Takai
    • Organizer
      International Conference on Organometallic Chemistry 2018 (ICOMC28)
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Molybdenum-Catalyzed Deoxygenative Cyclization of Carbonyl Compounds2018

    • Author(s)
      Sobi Asako, Seina Ishihara, Keiya Hirata, Kazuhiko Takai
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] タングステン触媒によるカルボニル化合物の脱酸素環化反応を利用するフルオレン合成2018

    • Author(s)
      平田佳也、石原聖奈、浅子壮美、高井和彦
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] モリブデン錯体を用いるカルボニル化合物の脱酸素を経る環化反応2017

    • Author(s)
      浅子壮美、石原聖奈、平田佳也、高井和彦
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Research-status Report
  • [Remarks]

    • URL

      http://achem.okayama-u.ac.jp/omc/

    • Related Report
      2019 Annual Research Report
  • [Remarks]

    • URL

      http://iliesteam.riken.jp/home_JP.html

    • Related Report
      2019 Annual Research Report
  • [Remarks]

    • URL

      http://achem.okayama-u.ac.jp/omc/

    • Related Report
      2017 Research-status Report

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Published: 2017-07-21   Modified: 2021-02-19  

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