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Development of the new palladium-catalyzed reactions including the construction of trifluoromethyl group by the intramolecular fluorine atom shift

Research Project

Project/Area Number 15K13701
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Synthetic chemistry
Research InstitutionNihon University

Principal Investigator

KAWATSURA Motoi  日本大学, 文理学部, 教授 (50360243)

Project Period (FY) 2015-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2016: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2015: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
Keywordsパラジウム / フッ素 / アミノ化 / アルキル化 / エーテル化 / トリフルオロメチル基 / エステル化
Outline of Final Research Achievements

We examined the reaction of 2,3,3-trifluoroallylic esters with several nucleophiles, such as nitrogen, oxygen, or carbon nucleophiles, by palladium catalysts, then we succeeded in progressing the new types of reactions, which provides trifluoromethyl group possessing organic compounds, which were produced by the attack of nucleophiles on to C-2 position of allylic group, and sequential intramolecular fluorine atom shift. We further demonstrated this types of palladium-catalyzed reaction with several types of nucleophiles, and succeeded in obtaining several types of trifluoromethylenamines, trifluoromethyl group containing 3-substituted indole analogues, or trifluoromethyl group possessing enol ethers.

Report

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

    (8 results)

All 2017 2015

All Journal Article (3 results) (of which Peer Reviewed: 3 results,  Acknowledgement Compliant: 2 results) Presentation (5 results) (of which Int'l Joint Research: 2 results)

  • [Journal Article] Intramolecular Construction of Trifluoromethyl Group by The Palladium-Catalyzed Alkylation of 2,3,3-Trifluoroallyl Esters with Indoles2017

    • Author(s)
      Hanakawa, T.; Isa, K.; Isobe, S.; Hoshino, Y.; Kawatsura, M.
    • Journal Title

      J. Org. Chem.

      Volume: 82 Issue: 4 Pages: 2281-2287

    • DOI

      10.1021/acs.joc.6b03085

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Ruthenium-catalyzed Regioselective Allylic Amination of 2,3,3-Tirfluoroallylic Carbonates2017

    • Author(s)
      Isobe, S.; Terasaki, S.; Hanakawa, T.; Mizuno, S.; Kawatsura, M.
    • Journal Title

      Org. Biomol. Chem.

      Volume: 15 Issue: 14 Pages: 2938-2946

    • DOI

      10.1039/c7ob00514h

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Palladium-Catalyzed Amination of 2,3,3-Trifluoroallyl Esters: Synthesis of Trifluoromethylenamines by the Intramolecular Fluorine Shift and CF3 Group Construction2015

    • Author(s)
      Isa, K.; Minakawa, M.; Kawatsura, M.
    • Journal Title

      Chem. Commun.

      Volume: 51 Issue: 31 Pages: 6761-6764

    • DOI

      10.1039/c5cc01212k

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Presentation] パラジウム触媒アミノ化反応による分子内トリフルオロメチル基構築を伴う四置換オレフィン合成2017

    • Author(s)
      大竹啓介,花川太駿,伊佐一希,川面 基
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應大学日吉キャンパス(神奈川県横浜市)
    • Year and Date
      2017-03-19
    • Related Report
      2016 Annual Research Report
  • [Presentation] パラジウム触媒による含フッ素アリルカーボネートと酸素求核剤との反応による分子内トリフルロメチル基の構築2017

    • Author(s)
      星野祐二,花川太駿,伊佐一希,川面 基
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應大学日吉キャンパス(神奈川県横浜市)
    • Year and Date
      2017-03-19
    • Related Report
      2016 Annual Research Report
  • [Presentation] パラジウム触媒による2,3,3-トリフルオロアリルカーボネートとアリールボロン酸との反応2017

    • Author(s)
      竹原生真,花川太駿,伊佐一希,川面 基
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應大学日吉キャンパス(神奈川県横浜市)
    • Year and Date
      2017-03-19
    • Related Report
      2016 Annual Research Report
  • [Presentation] Palladium-Catalyzed Amination 2,3,3-Trifluoroallyl Acetates with Amines: Synthesis of Trifluoromethylenamines2015

    • Author(s)
      Taisyun Hanakawa, Kazuki Isa, Maki Minakawa, Motoi Kawatsura
    • Organizer
      The 13th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC 13)
    • Place of Presentation
      Kyoto,
    • Year and Date
      2015-11-11
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Palladium-catalyzed Amination of 2,3,3-Trifluoroallyl Acetates with Amines, and Synthesis of Trifluoromethylenamines2015

    • Author(s)
      Taisyun HANAKAWA, Kazuki, ISA, Maki MINAKAWA, and Motoi KAWATSURA
    • Organizer
      18th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 18)
    • Place of Presentation
      Sitges-Barcelona, Spain
    • Year and Date
      2015-07-01
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research

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Published: 2015-04-16   Modified: 2018-03-22  

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