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Electrophilic activation and reactivity control of fluorinated alkenes by transition-metal complexes

Research Project

Project/Area Number 23655028
Research Category

Grant-in-Aid for Challenging Exploratory Research

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

Principal Investigator

ICHIKAWA Junji  筑波大学, 数理物質系, 教授 (70184611)

Project Period (FY) 2011 – 2012
Project Status Completed (Fiscal Year 2012)
Budget Amount *help
¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2012: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2011: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywordsジフルオロアルケン / パラジウム / 触媒 / 求電子的活性化 / フッ素 / 多環式芳香族炭化水素 / PAH / 有機半導体
Research Abstract

We have found that treatment of 1,1-difluoro-1-alkenes (or 1,1,2-trifluoro-1-alkenes) bearing a biphenyl skeleton with cationic Pd(II) catalysts, generated from palladium(II) chloride and silver salts, smoothly affords fluorinated (or difluorinated) phenanthrene derivatives. In this process, the fluorinated alkene moieties seem to be electrophilically activated through π coordination to Pd(II) center, which promotes Friedel-Crafts-type cyclizations to give the products.Regioselective syntheses of fluorinated polycyclic aromatic hydrocarbons (F-PAHs) have been accomplished by our catalytic process starting from well-designed 1,1-difluoro-1-alkenes.

Report

(3 results)
  • 2012 Annual Research Report   Final Research Report ( PDF )
  • 2011 Research-status Report
  • Research Products

    (41 results)

All 2013 2012 2011 Other

All Journal Article (15 results) (of which Peer Reviewed: 15 results) Presentation (22 results) (of which Invited: 2 results) Remarks (3 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Nucleophilic 5-endo-trig Cyclization of 3,3-Difluoroallylic Ketone Enolates: Synthesis of 5-Fluorinated 2-Alkylidene-2,3-dihydrofurans2013

    • Author(s)
      Fujita, T.; Sakoda, K.; Ikeda, M.; Hattori, M.; Ichikawa. J
    • Journal Title

      Synlett.

      Volume: 24 Issue: 01 Pages: 57-60

    • DOI

      10.1055/s-0032-1317709

    • NAID

      120007130513

    • URL

      https://www.thieme-connect.com/ejournals/abstract/10.1055/s-0032-1317709

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Substitutions of Two Fluorines in a Trifluoromethyl Group: Regioselective Synthesis of 3-Fluoropyrazoles2012

    • Author(s)
      Fuchibe, K.; Takahashi, M.; Ichikawa, J.
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 51 Issue: 48 Pages: 12059-12062

    • DOI

      10.1002/anie.201206946

    • Related Report
      2012 Annual Research Report 2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] γ-Selective Addition to 1,1-Difluoroallenes: Three-Component Coupling Leading to 2,2-Disubstituted 1,1-Difluoroalkenes2012

    • Author(s)
      Fuchibe, K.; Ueda, M.; Yokota, M.; Ichikawa, J
    • Journal Title

      Chem. Lett

      Volume: 41 Issue: 12 Pages: 1619-1621

    • DOI

      10.1246/cl.2012.1619

    • NAID

      10031135770

    • Related Report
      2012 Annual Research Report 2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] 1,1-Difluoro-1-alkenes as New Electrolyte Additives for Lithium Ion Batteries2012

    • Author(s)
      Kubota, T.; Ihara, M.; Katayama, S.; Nakai, H.; Ichikawa, J
    • Journal Title

      J. Power Sources

      Volume: 207 Pages: 141-149

    • DOI

      10.1016/j.jpowsour.2012.01.139

    • NAID

      120007130633

    • Related Report
      2012 Annual Research Report 2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Facile Synthesis of Substituted1, 1-Difluoroallenes via CarbonylDifluorovinylidenation2012

    • Author(s)
      Oh, K.; Fuchibe, K.; Yokota, M.; Ichikawa, J.
    • Journal Title

      Synthesis

      Volume: 44 Issue: 06 Pages: 857-861

    • DOI

      10.1055/s-0031-1290157

    • Related Report
      2012 Annual Research Report 2012 Final Research Report 2011 Research-status Report
    • Peer Reviewed
  • [Journal Article] NHC-Catalyzed Generation of Difluorocarbene and its Application to Difluoromethylation of Oxygen Nucleophiles2012

    • Author(s)
      Fuchibe, K., Koseki, Y., Aono, T., Sasagawa, H., Ichikawa, J
    • Journal Title

      J. Fluorine Chem

      Volume: 133 Pages: 52-60

    • DOI

      10.1016/j.jfluchem.2011.09.012

    • NAID

      120007130701

    • Related Report
      2012 Annual Research Report 2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] J. NHC-Catalyzed Difluorocarbene Generation and Its Application to Aryl Difluoromethyl Ether Synthesis2011

    • Author(s)
      Fuchibe, K.; Koseki, Y.; Sasagawa, H.; Ichikawa
    • Journal Title

      Chem. Lett

      Volume: 40 Issue: 10 Pages: 986-988

    • DOI

      10.1246/cl.2011.1189

    • NAID

      10029683941

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Facile Synthesis of β,β-Difluorostyrenes via the Negishi Coupling of Thermally Stable 2,2-Difluorovinyl Zinc-TMEDA Complex2011

    • Author(s)
      Fujita, T.; Ichitsuka, T.; Fuchibe, K.; Ichikawa, J.
    • Journal Title

      Chem.Lett.

      Volume: 40 Issue: 9 Pages: 986-988

    • DOI

      10.1246/cl.2011.986

    • NAID

      10029522357

    • URL

      https://www.jstage.jst.go.jp/article/cl/40/9/40_9_986/_article

    • Related Report
      2012 Final Research Report 2011 Research-status Report
    • Peer Reviewed
  • [Journal Article] J Facile Synthesis of β, β-Difluorostyrenes via the Negishi Coupling of Thermally Stable 2, 2-Difluorovinyl Zinc-TMEDA Complex2011

    • Author(s)
      Fujita, T.; Ichitsuka, T.; Fuchibe, K.; Ichikawa
    • Journal Title

      Chem. Lett

      Volume: 40 Issue: 43 Pages: 986-988

    • DOI

      10.1002/chem.201100618

    • Related Report
      2012 Final Research Report 2011 Research-status Report
    • Peer Reviewed
  • [Journal Article] Illusory Molecular Expression of "Penrose Stairs" by an Aromatic Hydrocarbon2011

    • Author(s)
      Nakanishi, W.; Matsuno, T.; Ichikawa, J.; Isobe, H
    • Journal Title

      Anegw. Chem. Int

      Volume: 50 Pages: 6048-6051

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] 5-Endo-Trig Cyclization of 1,1-Difluoro-1-Alkenes: Synthesis of 3-Butyl-2-Fluoro-1-Tosylindole (1H-Indole, 3-Butyl-2-Fluoro-1-[(4-Methylphenyl)Sulfonyl]-)2011

    • Author(s)
      Ichikawa, J
    • Journal Title

      Org. Synth

      Volume: 88 Pages: 162-167

    • URL

      http://www.orgsyn.org/orgsyn/default.asp?dbname=orgsyn&dataaction=search&metadata_directive=blind_gui&formgroup=quick_form_group&Preps.AnnVol=88&Preps.AnnPage=162&Preps.Published=1&order_by=Preps.AnnPage%20ASC

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of 1, 1-Difluoroallenes from Commercially Available 1, 1, 1-Trifluoro-2-iodoethane2011

    • Author(s)
      Oh, K.; Fuchibe, K.; Ichikawa, J
    • Journal Title

      Synthesis

      Volume: 2011 Issue: 06 Pages: 881-886

    • DOI

      10.1055/s-0030-1258438

    • Related Report
      2012 Final Research Report 2011 Research-status Report
    • Peer Reviewed
  • [Journal Article] Illusory molecular expression of "Penrose stairs" by an aromatic hydrocarbon2011

    • Author(s)
      Nakanishi, W.; Matsuno, T.; Ichikawa, J.; Isobe, H.
    • Journal Title

      Angew.Chem.Int.Ed.

      Volume: 50 Issue: 27 Pages: 6048-6051

    • DOI

      10.1002/anie.201102210

    • Related Report
      2011 Research-status Report
    • Peer Reviewed
  • [Journal Article] Domino Synthesis of Fluorine-Substituted PAHs: 1,1-Difluoroallenes as Synthetic Platforms

    • Author(s)
      Fuchibe, K.; Mayumi, Y.; Zhao, N.; Watanabe, S.; Yokota, M.; Ichikawa. J
    • Journal Title

      Angew. Chem. Int

      Volume: (in press)

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Journal Article] Redox switching of conjugationlength using 9,9,10,10-tetraaryl-9,10-dihydrophenanthrene as an ON/OFF unit: Preparation, X-ray structure, and redox properties of perfluorobiphenyl derivative and its SNAr reactions to π-extended analogues

    • Author(s)
      Suzuki, T.; Tamaoki, H.; Katoono, R; Fujiwara, K.; Ichikawa. J.; Fukushima, T.
    • Journal Title

      Chem. Lett

      Volume: (in press)

    • URL

      http://dx.doi.org/10.1246/cl.130190

    • Related Report
      2012 Final Research Report
    • Peer Reviewed
  • [Presentation] Construction of fluorinated heterocycles: Intramolecular substitution of vinylic and allylic fluorines2013

    • Author(s)
      Ichikawa, J
    • Organizer
      245th ACS National Meeting & Exposition
    • Place of Presentation
      New Orleans, U.S.A
    • Year and Date
      2013-04-08
    • Related Report
      2012 Final Research Report
  • [Presentation] Electrophilic Activation and Cyclization of Fluoro Alkenes Directed toward PAH Synthesis2012

    • Author(s)
      Ichikawa, J
    • Organizer
      Dasan Conference 2012: Green Chemical Industry for Enviroment and Health: Fluorine Conpounds
    • Place of Presentation
      Changwon, Republic of Korea
    • Year and Date
      2012-11-15
    • Related Report
      2012 Final Research Report
  • [Presentation] Facile Synthesis of Fluorinated Benzoheterole Derivatibes via Regioselective Allylic Substituion of 3-Bromo-3,3-difluoropropene2012

    • Author(s)
      Sugiyama, K.; Sanada, S.; Chiba, Y.: Fujita, T、Ichikawa, J
    • Organizer
      IKCOC-12
    • Place of Presentation
      京都市, リーガロイヤルホテル京都
    • Year and Date
      2012-11-14
    • Related Report
      2012 Final Research Report
  • [Presentation] NHC-Catalyzed Generation of Difluorocarbene: Syntheses of Aryl Difluoromethyl Ethers and Difluoromethyl Imidates2012

    • Author(s)
      Fuchibe, K.; Koseki, Y.; Aono, T.; Ichikawa, J
    • Organizer
      4th Asian Silicon Symposium
    • Place of Presentation
      つくば市, つくば国際会議場
    • Year and Date
      2012-10-22
    • Related Report
      2012 Final Research Report
  • [Presentation] Synthesis of fluorinated PAHs by one-pot reactions of difluoroallenes2012

    • Author(s)
      Fuchibe, K.; Zhao, N.; Ichikawa, J
    • Organizer
      20th International Symposium on Fluorine Chemistry
    • Place of Presentation
      京都市, 京都テルサ
    • Year and Date
      2012-07-26
    • Related Report
      2012 Final Research Report
  • [Presentation] Regioselectivity-switchable allylic substitution of 3-bromo-3,3-difluoropropene with heteronucleophiles toward syntheses of fluorinated dihydrobenzoheteroles2012

    • Author(s)
      Sugiyama, K.; Sanada, S.; Chiba, Y.; Fujita, T.; Ichikawa, J.
    • Organizer
      20th International Symposium on Fluorine Chemistry
    • Place of Presentation
      京都市, 京都テルサ
    • Year and Date
      2012-07-24
    • Related Report
      2012 Final Research Report
  • [Presentation] Synthesis of substituted F-PAHs: Palladium(II)-catalyzed Friedel-Crafts-type cyclizations of 1,1-difluoro-1-alkenes via their electrophilic activation2012

    • Author(s)
      Ueda, R.; Morikawa, T.; Tanabe, H.; Fuchibe, K.; Ichikawa, J
    • Organizer
      20th International Symposium on Fluorine Chemistry
    • Place of Presentation
      京都市, 京都テルサ
    • Year and Date
      2012-07-24
    • Related Report
      2012 Final Research Report
  • [Presentation] Construction of Fluorinated Heterocycles: Intramolecular Substitution of Vinylic and Allylic Fluorines2012

    • Author(s)
      Ichikawa, J
    • Organizer
      8th Japanese-French Joint Seminar on Fluorine Chemistry
    • Place of Presentation
      京都市, 大谷婦人会館
    • Year and Date
      2012-07-21
    • Related Report
      2012 Final Research Report
  • [Presentation] Difluoroallene Chemistry: Preparation and Application", [Invited] 3rd International Symposium on Organofluorine Compounds in Biomedical2012

    • Author(s)
      Ichikawa, J
    • Organizer
      Materials and Agricultural Sciences
    • Place of Presentation
      Valencia,Spain
    • Year and Date
      2012-06-21
    • Related Report
      2012 Final Research Report
  • [Presentation] フルオロアルケンの求電子的活性化と環構築2012

    • Author(s)
      市川淳士
    • Organizer
      平成24年度前期(春季)有機合成化学講習会
    • Place of Presentation
      東京都、長井記念ホール
    • Year and Date
      2012-06-20
    • Related Report
      2012 Final Research Report
  • [Presentation] Electrophilic Cyclization of Fluoro Alkenes Directed toward PAH Synthesis2011

    • Author(s)
      Ichikawa, J.
    • Organizer
      1st International Symposium on Creation of Functional Materials
    • Place of Presentation
      つくば市, 筑波大学大学会館
    • Year and Date
      2011-12-18
    • Related Report
      2012 Final Research Report
  • [Presentation] Sequential Substitutions of 2-Trifluoromethyl-1-alkenes: Regioselective Synthesis of 3-Fluoropyrazoles2011

    • Author(s)
      Takahashi, M.; Hattori, M.; Fuchibe, K.; Ichikawa, J
    • Organizer
      ISOR-10
    • Place of Presentation
      横浜市, 慶応義塾大学日吉キャンパス
    • Year and Date
      2011-11-02
    • Related Report
      2012 Final Research Report
  • [Presentation] Metal-Catalyzd Domino Difluorocyclopropanation-Ring Expansion of 2-Siloxy-1,3-dienes: Synthesis of Fluorinated Cyclic Silyl Enol Ethers2011

    • Author(s)
      Aono, T.; Sasagawa, H.; Fuchibe, K.; Ichikawa, J.
    • Organizer
      ISOR-10
    • Place of Presentation
      横浜市, 慶応義塾大学日吉キャンパス
    • Year and Date
      2011-11-02
    • Related Report
      2012 Final Research Report
  • [Presentation] Synthesis of F-PAHs by In(III)-Catalyzed Domino Cyclization-Ring Expansion of 1,1-Difluoroallenes2011

    • Author(s)
      Fuchibe, K.; Zhao, N.; Mayumi, Y.; Ichikawa, J
    • Organizer
      ISIS-7
    • Place of Presentation
      神戸市, シーサイドホテル舞子ビラ神戸
    • Year and Date
      2011-10-10
    • Related Report
      2012 Final Research Report
  • [Presentation] Electrophilic Cyclization of Fluoro Alkenes Directed toward PAH Synthesis2011

    • Author(s)
      Ichikawa, J.
    • Organizer
      242nd ACS National Meeting
    • Place of Presentation
      Denver,U.S.A
    • Year and Date
      2011-08-28
    • Related Report
      2012 Final Research Report
  • [Presentation] Electrophilic Cyclization of Fluoro Alkenes Directed toward PAH Synthesis2011

    • Author(s)
      Ichikawa, J
    • Organizer
      NTU-JSPS Joint Symposium
    • Place of Presentation
      Singapore
    • Year and Date
      2011-08-02
    • Related Report
      2012 Final Research Report
  • [Presentation] In(III)-Catalyzed Synthesis of F-PAHs: Domino Cyclization-Ring Expansion Reactions of 1,1-Difluoroallenes2011

    • Author(s)
      Fuchibe, K.; Zhao, N.; Mayumi, Y.; Ichikawa, J
    • Organizer
      OMCOS-16
    • Place of Presentation
      Shanghai, China
    • Year and Date
      2011-07-24
    • Related Report
      2012 Final Research Report
  • [Presentation] Electrophilic Cyclization of Fluoro Alkenes Directed toward PAH Synthesis2011

    • Author(s)
      Ichikawa, J.
    • Organizer
      NTU-JSPS JOINT SEMINAR 2011(招待講演)
    • Place of Presentation
      Singapore, Singapore
    • Related Report
      2011 Research-status Report
  • [Presentation] Electrophilic Cyclization of Fluoro Alkenes Directed toward PAH Synthesis2011

    • Author(s)
      Ichikawa, J.
    • Organizer
      242nd ACS National Meeting(招待講演)
    • Place of Presentation
      Denver, U.S.A
    • Related Report
      2011 Research-status Report
  • [Presentation] Difluoroallene Chemistry: Preparation and Application.

    • Author(s)
      Ichikawa, J.
    • Organizer
      3rd International Symposium on Organofluorine Compounds in Biomedical, Materials and Agricultural Sciences
    • Place of Presentation
      Valencia, Spain
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Presentation] Construction of Fluorinated Heterocycles: Intramolecular Substitution of Vinylic and Allylic Fluorines

    • Author(s)
      Ichikawa, J.
    • Organizer
      8th Japanese-French Joint Seminar on Fluorine Chemistry
    • Place of Presentation
      Kyoto, Japan
    • Related Report
      2012 Annual Research Report
  • [Presentation] Electrophilic Activation and Cyclization of Fluoro Alkenes Directed toward PAH Synthesis

    • Author(s)
      Ichikawa, J.
    • Organizer
      Dasan Conference 2012
    • Place of Presentation
      Dasan, Korea
    • Related Report
      2012 Annual Research Report
    • Invited
  • [Remarks]

    • URL

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

    • Related Report
      2012 Final Research Report
  • [Remarks] 市川淳士研究室 ウェブサイト

    • URL

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

    • Related Report
      2012 Annual Research Report
  • [Remarks]

    • URL

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

    • Related Report
      2011 Research-status Report
  • [Patent(Industrial Property Rights)] 含フッ素化合物および該含フッ素化合物を用いた有機薄膜トランジスタ2013

    • Inventor(s)
      市川淳士、山本今日子
    • Industrial Property Rights Holder
      瀧川具也
    • Industrial Property Number
      2013-007148
    • Filing Date
      2013-01-18
    • Related Report
      2012 Final Research Report

URL: 

Published: 2011-08-05   Modified: 2019-07-29  

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