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Systematic Synthesis of Fluorine-Containing Compounds via Transition Metal-Catalyzed Fluorine Elimination

Research Project

Project/Area Number 16K20939
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Organic chemistry
Synthetic chemistry
Research InstitutionUniversity of Tsukuba

Principal Investigator

FUJITA Takeshi  筑波大学, 数理物質系, 助教 (60603066)

Project Period (FY) 2016-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2017: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2016: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Keywords有機合成化学 / フッ素 / 金属触媒 / 有機金属化学 / 触媒 / 有機化学
Outline of Final Research Achievements

I established a methodology for the catalytic synthesis of fluorine-containing compounds by applying metal-mediated fluorine elimination to a wide variety of organometallic reactions. Rational combination of typical organometallic elementary steps with fluorine elimination processes enabled catalytic C-F bond activation. Herein, I mainly utilized (i) electrophilic activation of unsaturated bonds, (ii) oxidative cyclization, and (iii) an oxidative addition-insertion sequence, for the setup of organometallic intermediates suitable for fluorine elimination. Although, in such cases, inert metal fluorides were formed during reactions, I succeeded in regeneration of catalytically active species by addition of appropriate reagents.

Report

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

    (32 results)

All 2018 2017 2016 Other

All Journal Article (11 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 11 results,  Open Access: 6 results,  Acknowledgement Compliant: 2 results) Presentation (16 results) (of which Int'l Joint Research: 2 results,  Invited: 2 results) Remarks (4 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Flash Generation and Borylation of 1-(trifluoromethyl)vinyllithium toward Synthesis of α-(trifluoromethyl)styrenes.2018

    • Author(s)
      Fujita, T.; Konno, N.; Watabe, Y.; Ichitsuka, T.; Nagaki, A.; Yoshida, J.; Ichikawa, J.
    • Journal Title

      J. Fluorine Chem.

      Volume: 207 Pages: 72-76

    • DOI

      10.1016/j.jfluchem.2018.01.004

    • NAID

      120007134197

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Nickel-Catalyzed Hydroalkenylation of Alkynes via C-F Bond Activation: Synthesis of 2-Fluoro- 1,3-dienes2017

    • Author(s)
      Watabe Yota、Kanazawa Kohei、Fujita Takeshi, Ichikawa Junji、
    • Journal Title

      Synthesis

      Volume: 49 Issue: 16 Pages: 3569-3575

    • DOI

      10.1055/s-0036-1588842

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Pinpoint-fluorinated Polycyclic Aromatic Hydrocarbons (F-PAHs): Syntheses of Difluorinated Subfamily and Their Properties2017

    • Author(s)
      Fuchibe Kohei、Shigeno Kento、Zhao Nan、Aihara Hiromichi、Akisaka Rikuo、Morikawa Toshiyuki、Fujita Takeshi、Yamakawa Kie、Shimada Toshihiro、Ichikawa Junji
    • Journal Title

      J. Fluorine Chem.

      Volume: 203 Pages: 173-184

    • DOI

      10.1016/j.jfluchem.2017.09.002

    • NAID

      120007134565

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Ring-Size-Selective Construction of Fluorine-Containing Carbocycles via Intramolecular Iodoarylation of 1,1-Difluoro-1-alkenes2017

    • Author(s)
      Fujita Takeshi、Kinoshita Ryo、Takanohashi Tsuyoshi、Suzuki Naoto、Ichikawa Junji
    • Journal Title

      Beil. J. Org. Chem.

      Volume: 13 Pages: 2682-2689

    • DOI

      10.3762/bjoc.13.266

    • NAID

      120007134607

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Facile Synthesis of Polycyclic Aromatic Hydrocarbons: Bronsted Acid-Catalyzed Dehydrative Cycloaromatization of Carbonyl Compounds in 1,1,1,3,3,3- Hexafluoropropan-2-ol2017

    • Author(s)
      Fujita, T.; Takahashi, I.; Hayashi, M.; Wang, J.; Fuchibe, K.; Ichikawa, J.
    • Journal Title

      European Journal of Organic Chemistry

      Volume: 2 Issue: 2 Pages: 262-265

    • DOI

      10.1002/ejoc.201601406

    • Related Report
      2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Domino C-F Bond Activation of the CF3 Group: Synthesis of Fluorinated Dibenzo[a,c][7]annulenes from 2-(Trifluoromethyl)-1-alkenes and 2,2′-Diceriobiaryls2017

    • Author(s)
      Takeshi Fujita, Marina Takazawa, Kazuki Sugiyama, Naoto Suzuki, Junji Ichikawa
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 3 Pages: 588-591

    • DOI

      10.1021/acs.orglett.6b03743

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Cell-quintupling: Structural phase transition in a molecular crystal, bis(trans-4'-butylcyclohexyl)methanol2017

    • Author(s)
      K. Saito, T. Ikeda, Y. Yamamura, H. Saitoh, M. Hishida, Y. Kobayashi, T. Fujita & J. Ichikawa
    • Journal Title

      J. Chem. Phys.

      Volume: 146 Issue: 7 Pages: 074503-074503

    • DOI

      10.1063/1.4976318

    • NAID

      120007134902

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Bronsted Acid-catalyzed Tandem Cycloaromatization of Naphthalene-based Bisacetals: Selective Synthesis of ortho-Fused Six-hexagon Benzenoids2017

    • Author(s)
      Ikko Takahashi, Masaki Hayashi, Takeshi Fujita, Junji Ichikawa
    • Journal Title

      Chemistry Letters

      Volume: 46 Issue: 3 Pages: 392-394

    • DOI

      10.1246/cl.161122

    • NAID

      130005436654

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthetic Methods for Ring-Fluorinated Pyrrole Derivatives2017

    • Author(s)
      Takeshi Fujita, Junji Ichikawa
    • Journal Title

      Heterocycles

      Volume: 95 Issue: 2 Pages: 694-714

    • DOI

      10.3987/rev-16-sr(s)6

    • Related Report
      2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Silver-catalyzed Vinylic C&ndash;F Bond Activation: Synthesis of 2-Fluoroindoles from &beta;,&beta;-Difluoro-<i>o</i>-sulfonamidostyrenes2016

    • Author(s)
      Fujita, T.; Watabe, Y.; Yamashita, S.; Tanabe, H.; Nojima, T.; Ichikawa, J.
    • Journal Title

      Chemistry Letters

      Volume: 45 Issue: 8 Pages: 964-966

    • DOI

      10.1246/cl.160427

    • NAID

      130005254491

    • ISSN
      0366-7022, 1348-0715
    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Aluminium-mediated Aromatic C-F Bond Activation: Regioswitchable Construction of Benzene-fused Triphenylene Frameworks2016

    • Author(s)
      Suzuki, N.; Fujita, T.; Amsharov, K.; Ichikawa, J.
    • Journal Title

      Chemical Communications

      Volume: 52 Issue: 88 Pages: 12948-12951

    • DOI

      10.1039/c6cc07199f

    • NAID

      120007129242

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Presentation] 金属触媒によるフッ素脱離を活用した炭素-フッ素結合活性化法 ~フロン類の有効再利用に向けて~2018

    • Author(s)
      藤田健志
    • Organizer
      K-CONNEXファーストコンタクトプログラム
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Defluorinative Arylation of Fluoroalkenes via Transition Metal-Catalyzed Fluorine Elimination2018

    • Author(s)
      Yota Watabe, Takeshi Fujita, Junji Ichikawa
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] ロジウム(I)触媒による炭素-酸素結合活性化を経由したビフェニレンと酢酸ビニルの[4+2]環化:置換フェナントレンの合成2018

    • Author(s)
      渡部陽太、武石匡史、藤田健志、市川淳士
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 環状共役トリエノンとボランによるトロピリウムの合成とその発光特性2017

    • Author(s)
      戸村文弥、藤田健志、市川淳士
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学、神奈川県横浜市
    • Year and Date
      2017-03-18
    • Related Report
      2016 Research-status Report
  • [Presentation] ブレンステッド酸触媒による不活性アルキンの分子内ヒドロアリール化:フェナセン類の高効率合成2017

    • Author(s)
      高橋一光、藤田健志、市川淳士
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学、神奈川県横浜市
    • Year and Date
      2017-03-17
    • Related Report
      2016 Research-status Report
  • [Presentation] 酸によるヘテロ芳香族炭素-フッ素結合活性化:縮合ヘテロ環化合物の合成2017

    • Author(s)
      福田拓也、鈴木直人、藤田健志、市川淳士
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学、神奈川県横浜市
    • Year and Date
      2017-03-17
    • Related Report
      2016 Research-status Report
  • [Presentation] ジフルオロホモアリル化合物の求核的5-endo-trig環化:フッ素置換ジヒドロヘテロールの合成2017

    • Author(s)
      藤田健志、森岡龍太郎、在田知央、市川淳士
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学、神奈川県横浜市
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] 不定形高次多環式芳香族炭化水素の合成法: TfOH-in-HFIP 触媒によるタンデム型芳香環増環法2017

    • Author(s)
      林雅樹、高橋一光、藤田健志、市川淳士
    • Organizer
      第73回有機合成化学協会関東支部シンポジウム
    • Related Report
      2017 Annual Research Report
  • [Presentation] 遷移金属によるフッ素脱離過程を活用したビニル位炭素-フッ素結合活性化:フルオロアレーン類の簡便合成法2017

    • Author(s)
      渡部陽太、市塚知宏、金沢康平、藤田健志、市川淳士
    • Organizer
      第111回有機合成シンポジウム
    • Related Report
      2017 Annual Research Report
  • [Presentation] ニッケル触媒によるβ-フッ素脱離を活用したアリルおよびビニル炭素-フッ素結合活性化:還元的カップリングとヒドロアルケニル化2017

    • Author(s)
      藤田健志、小林優太郎、金沢康平、渡部陽太、市塚知宏、高橋一光、市川淳士
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Ni触媒を用いたアリル位およびビニル位C-F結合活性化を経るフルオロアルケン合成2017

    • Author(s)
      渡部陽太、小林優太郎、金沢康平、藤田健志、市川淳士
    • Organizer
      第40回フッ素化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] フロンガスの有効再利用を指向した触媒的炭素-フッ素結合活性化法2017

    • Author(s)
      藤田健志
    • Organizer
      CUPALワークショップ
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] ブレンステッド酸触媒によるカチオン環化反応を用 いたタンデム型芳香環増環法2016

    • Author(s)
      林雅樹、高橋一光、藤田健志、市川淳士
    • Organizer
      第6回CSJ化学フェスタ
    • Place of Presentation
      タワーホール船堀、東京都江戸川区
    • Year and Date
      2016-11-16
    • Related Report
      2016 Research-status Report
  • [Presentation] Silver-Catalyzed Vinylic C-F Bond Activation: Synthesis of 2-Fluoroindoles from β,β-Difluoro-o-Sulfonamidostyrenes2016

    • Author(s)
      渡部陽太、山下茂之、野島智也、藤田健志、市川淳士
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      早稲田大学、東京都新宿区
    • Year and Date
      2016-09-14
    • Related Report
      2016 Research-status Report
  • [Presentation] Nickel-Catalyzed Hydroalkenylation of Alkynes via C-F Bond Activation: 2-Fluoro-1,3-diene Synthesis2016

    • Author(s)
      Kohei Kanazawa, Yota Watabe, Takeshi Fujita, Junji Ichikawa
    • Organizer
      20th International Symposium on Homogeneous Catalysis
    • Place of Presentation
      京都テルサ、京都府京都市
    • Year and Date
      2016-07-14
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] 2-Fluoroindole Synthesis via Silver-Catalyzed 5-endo-trig Cyclization of β,β-Difluorostyrenes2016

    • Author(s)
      Yota Watabe, Shigeyuki Yamashita, Tomoya Nojima, Takeshi Fujita, Junji Ichikawa
    • Organizer
      The 12th International Symposium on Organic Reactions
    • Place of Presentation
      京都テルサ、京都府京都市
    • Year and Date
      2016-04-23
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Remarks] TRIOS

    • URL

      http://www.trios.tsukuba.ac.jp/researcher/0000000665

    • Related Report
      2017 Annual Research Report
  • [Remarks] ORCID

    • URL

      https://orcid.org/0000-0001-9666-022X

    • Related Report
      2017 Annual Research Report
  • [Remarks] ResearcherID

    • URL

      http://www.researcherid.com/rid/Q-5564-2017

    • Related Report
      2017 Annual Research Report
  • [Remarks] 市川淳士研究室ウェブサイト

    • URL

      http://www.chem.tsukuba.ac.jp/junji_lab/index.html

    • Related Report
      2017 Annual Research Report
  • [Patent(Industrial Property Rights)] 1、1、1、3、3、3-ヘキサフルオロプロパン-2-オールと脂肪族炭化水素系溶媒を用いた二相系反応媒体2017

    • Inventor(s)
      市川淳士、藤田健志、高橋一光
    • Industrial Property Rights Holder
      市川淳士、藤田健志、高橋一光
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2017-039790
    • Filing Date
      2017
    • Related Report
      2017 Annual Research Report

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Published: 2016-04-21   Modified: 2019-12-27  

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