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Mechanistic Studies and Development of Catalytic Palladium Enolate Umpolung Reactions

Research Project

Project/Area Number 18K05105
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionKagawa National College of Technology (2019-2021)
Osaka University (2018)

Principal Investigator

Takenaka Kazuhiro  香川高等専門学校, 一般教育科(詫間キャンパス), 講師 (20423113)

Project Period (FY) 2018-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2020: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2018: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Keywordsパラジウム触媒 / エノラート / 極性転換 / カルボニル化合物 / 反応機構
Outline of Final Research Achievements

Palladium enolates, which commonly act as nucleophiles, are known to react with an electrophile. We have succeeded in the development of new catalytic reactions involving nucleophilic interception of the palladium enolate. This umpolung process furnishes an efficient route to densely functionalized carbonyl compounds by way of ring-closing carbon-carbon bond formation and subsequent nucleophilic attack at the resulting palladium enolate intermediate. It is also revealed that fine-tuning of the electron density on the palladium complex is crucial for this enolate umpolung process.

Academic Significance and Societal Importance of the Research Achievements

アミノ酸のようなカルボニル基のα位に官能基をもつ化合物は、医薬品や農薬など様々な製品に利用され、現代生活の基盤を支える重要な物質である。本研究では常識にとらわれず、一般的に知られた反応性を逆転させることで新しい反応を実現した。見出した成果は、画期的な合成戦略の提案、生産コストの削減や新規化合物の設計といったカルボニル化合物の製造に多大な影響をもたらすと期待できる。

Report

(5 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Research-status Report
  • 2019 Research-status Report
  • 2018 Research-status Report
  • Research Products

    (18 results)

All 2022 2020 2019 2018

All Journal Article (5 results) (of which Peer Reviewed: 5 results) Presentation (13 results) (of which Int'l Joint Research: 3 results)

  • [Journal Article] Preparation of a Water Gauge and its Application to the Measurements of Water Level as a Teaching Tool of Experiments in Engineering2022

    • Author(s)
      矢野潤,松田雄二,橋本千尋,多田佳織,伊藤武志,岡野寛,立川直樹,竹中和浩,村上清久
    • Journal Title

      Journal of JSEE

      Volume: 70 Issue: 2 Pages: 2_20-2_24

    • DOI

      10.4307/jsee.70.2_20

    • ISSN
      1341-2167, 1881-0764
    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Allylamine Derivatives via Intermolecular Aza-Wacker-Type Reaction Promoted by Palladium-SPRIX Catalyst2020

    • Author(s)
      Sen, A.; Zhu, L.; Takizawa, S.; Takenaka, K.; Sasai, H.
    • Journal Title

      Adv. Synth. Catal.

      Volume: 362 Issue: 17 Pages: 3558-3563

    • DOI

      10.1002/adsc.202000644

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Enantioselective One-pot Synthesis of 3-Azabicyclo[3.1.0]hexanes via Allylic Substitution and Oxidative Cyclization2020

    • Author(s)
      Chaki, B. M.; Takenaka, K.; Zhu, L.; Tsujihara, T.; Takizawa, S.; Sasai, H.
    • Journal Title

      Adv. Synth. Catal.

      Volume: 362 Issue: 7 Pages: 1537-1547

    • DOI

      10.1002/adsc.202000044

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Enantioselective synthesis of spiro (isoxazole-isoxazoline) hybrid ligands2018

    • Author(s)
      B. M. Chaki, K. Wakita, S. Takizawa, K. Takenaka, H. Sasai
    • Journal Title

      Heterocycles

      Volume: - Issue: 1 Pages: 493-505

    • DOI

      10.3987/com-18-s(t)41

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Aza-Wacker-Type Cyclization Promoted by Pd-SPRIX Catalyst2018

    • Author(s)
      Sen, A.; Takenaka, K.; Sasai, H.
    • Journal Title

      Org. Lett.

      Volume: 20 Issue: 21 Pages: 6827-6831

    • DOI

      10.1021/acs.orglett.8b02946

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Presentation] Palladium Enolate Umpolung: Cyclative Hydroamination of Alkynyl Cyclohexadienones2019

    • Author(s)
      Kusaba, M.; Nomoto, Y.; Takenaka, K.; Sasai, H.
    • Organizer
      20th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS20)
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Palladium Enolate Umpolung ~ take the sweet with the sour ~2019

    • Author(s)
      竹中和浩
    • Organizer
      触媒有機化学セミナー
    • Related Report
      2019 Research-status Report
  • [Presentation] パラジウムエノラートの極性転換型求核的アミノ化反応の開発2019

    • Author(s)
      草場未来,野本裕也,竹中和浩,笹井宏明
    • Organizer
      第52回有機金属若手夏の学校
    • Related Report
      2019 Research-status Report
  • [Presentation] カリックスアレーン,ピンサー,スピロ,合言葉はパラジウム2019

    • Author(s)
      竹中和浩
    • Organizer
      第1回Central Science Symposium
    • Related Report
      2019 Research-status Report
  • [Presentation] Facile Synthesis of Allylamines via Intermolecular Aza-Wacker-Type Reaction Promoted by a Pd-SPRIX Catalyst2019

    • Author(s)
      Abhijit Sen、竹中和浩、笹井宏明
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Effect of Phosphine Ligands on Pd-catalyzed Cyclative Hydroamination2019

    • Author(s)
      草場未来、竹中和浩、笹井宏明
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Development of New Chiral Ligands Based on a Tetraphenylene Backbone2019

    • Author(s)
      片岡航佑、竹中和浩、笹井宏明
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Enantioselective Synthesis of Bicyclic Pyrrolidine Derivatives via One-Pot Sequential Organo and Palladium Catalysis2018

    • Author(s)
      Chaki, B. M.; Zhu, L.; Takenaka, K.; Bai, J.; Takizawa, S.; Sasai, H.
    • 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] Catalytic Cyclative Hydroamination Based on Palladium Enolate Umpolung2018

    • Author(s)
      Nomoto, Y.; Kusaba, M.; Takenaka, K.; Sasai, H.
    • Organizer
      International Research Training Group “SELECTIVITY IN CHEMO- AND BIOCATALYSIS” FINAL AACHEM-OSAKA SYMPOSIUM
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] 有機分子-パラジウム連続触媒反応を活用する二環式ピロリジン誘導体のエナンチオ選択的ワンポット合成2018

    • Author(s)
      竹中和浩、Bijan Mohon Chaki、Jianfei Bai、滝澤忍、笹井宏明
    • Organizer
      Symposium on Molecular Chirality 2018
    • Related Report
      2018 Research-status Report
  • [Presentation] 連続触媒プロセスによる二環式ピロリジン誘導体のエナンチオ選択的ワンポット合成2018

    • Author(s)
      竹中和浩、Bijan Mohon Chaki、Jianfei Bai、滝澤忍、笹井宏明
    • 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] エナンチオ選択的パラジウム2価ー4価触媒反応を基盤とする二環式ピロリジン誘導体のワンポット合成2018

    • Author(s)
      竹中和浩、Bijan Mohon Chaki、Linpeng ZHU、Jianfei Bai、滝澤忍、笹井宏明
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] Pd-SPRIX触媒を用いるaza-Wacker型反応の開発2018

    • Author(s)
      Abhijit Sen、竹中和浩、笹井宏明
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Research-status Report

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Published: 2018-04-23   Modified: 2023-01-30  

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