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Catalytic Syntheses of Organofluorine Compounds Based on Fluorine-Substituted Complexes

Research Project

Project/Area Number 15K05414
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Organic chemistry
Research InstitutionUniversity of Tsukuba

Principal Investigator

FUCHIBE Kohei  筑波大学, 数理物質系, 准教授 (10348493)

Project Period (FY) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2017: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
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触媒 / フッ素 / カルベン錯体 / 医薬 / 農薬 / ニッケル / 銅 / ビニリデン / カルベン / フルオロアルケン / シリルエノールエーテル / 付加環化 / シクロプロパン
Outline of Final Research Achievements

Organofluorine compounds have increased their importance as pharmaceuticals and agrochemicals especially in recent years. We have focused our attention on difluorocarbene complexes that realize highly efficient syntheses of organofluorine compounds with metal catalysts. It was disclosed that nickel(II) and copper(I) complexes generate the corresponding difluorocarbene complexes and that selective syntheses of isomeric α,α- and β,β-difluorocyclopentanone derivatives, starting from common silyl dienol ethers, were facilitated. The structures which we successfully constructed in this project were commonly found in those of biologically active compounds, leading to development and efficient manufacturing of pharmaceuticals and agrochemicals in future.

Report

(4 results)
  • 2017 Annual Research Report   Final Research Report ( PDF )
  • 2016 Research-status Report
  • 2015 Research-status Report
  • Research Products

    (42 results)

All 2018 2017 2016 2015 Other

All Journal Article (14 results) (of which Peer Reviewed: 14 results,  Open Access: 2 results,  Acknowledgement Compliant: 1 results) Presentation (25 results) (of which Int'l Joint Research: 4 results,  Invited: 8 results) Book (2 results) Remarks (1 results)

  • [Journal Article] Lewis Acid-Promoted Single C-F Bond Activation of the CF3 Group: SN1'-type 3,3- Difluoroallylation of Arenes with 2-Trifluoromethyl-1-alkenes2017

    • Author(s)
      Fuchibe Kohei、Hatta Hibiki、Oh Ken、Oki Rie、Ichikawa Junji
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 56 Issue: 21 Pages: 5890-5893

    • DOI

      10.1002/anie.201701985

    • Related Report
      2017 Annual Research Report 2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Pinpoint-fluorinated Polycyclic Aromatic Hydrocarbons: Benzene Ring Extension Cycle Involving Microwave-assisted SNAr Reaction2017

    • Author(s)
      Fuchibe Kohei、Imaoka Hisanori、Ichikawa Junji
    • Journal Title

      Chem. Asian J.

      Volume: 12 Issue: 18 Pages: 2359-2363

    • DOI

      10.1002/asia.201700870

    • NAID

      120007134792

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Sulfanylated Difluoroalkenes: Electrophilic Difluoromethylidenation of Dithioesters with Difluorocarbene2017

    • Author(s)
      Takayama Ryo、Yamada Atsushi、Fuchibe Kohei、Ichikawa Junji
    • Journal Title

      Org. Lett.

      Volume: 19 Issue: 19 Pages: 5050-5053

    • DOI

      10.1021/acs.orglett.7b02222

    • 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] Regioselective Syntheses of Fluorinated Cyclopentanone Derivatives: Ring Construction Strategy Using Transition-Metal-Difluorocarbene Complexes and Free Difluorocarbene2017

    • Author(s)
      Fuchibe Kohei、Takayama Ryo、Aono Tatsuya、Hu Ji、Hidano Tomohiro、Sasagawa Hisashi、Fujiwara Masaki、Miyazaki Shinji、Nadano Ryo, Ichikawa Junji
    • Journal Title

      Synthesis

      Volume: 50 Issue: 03 Pages: 514-528

    • DOI

      10.1055/s-0036-1591728

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Metal-free Synthesis of α,α-Difluorocyclopentanone Derivatives via Regioselective Difluorocyclopropanation/VCP Rearrangement of Silyl Dienol Ethers2017

    • Author(s)
      Takayama Ryo、Fuchibe Kohei、Ichikawa Junji
    • Journal Title

      Arkivoc

      Volume: ⅱ Issue: 2 Pages: 72-80

    • DOI

      10.24820/ark.5550190.p010.290

    • NAID

      120007133816

    • 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] Regioselective Synthesis of α-Fluorinated Cyclopentenones via Organocatalytic Difluorocyclopropanation and Fluorine-Directed and -Activated Nazarov Cyclization2017

    • Author(s)
      Fuchibe, K.; Takayama, R.; Yokoyama, T.; Ichikawa, J.
    • Journal Title

      Chemistry A European Journal

      Volume: 23 Issue: 12 Pages: 2831-2838

    • DOI

      10.1002/chem.201604578

    • Related Report
      2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Copper(I)-Catalyzed [4 + 1] Cycloaddition of Silyl Dienol Ethers with Sodium Bromodifluoroacetate: Access to β,β-Difluorocyclopentanone Derivatives2016

    • Author(s)
      Fuchibe, K.; Aono, T.; Hu, J.; Ichikawa, J.
    • Journal Title

      Organic Letters

      Volume: 18 Issue: 18 Pages: 4502-4505

    • DOI

      10.1021/acs.orglett.6b02085

    • Related Report
      2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Preparation of 1,1-Difluoroallenes by Difluorovinylidenation of Carbonyl Compounds2016

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

      Organic Syntheses

      Volume: 93 Pages: 352-366

    • Related Report
      2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Organocatalytic, Difluorocarbene-Based S-Difluoromethylation of Thiocarbonyl Compounds2015

    • Author(s)
      Fuchibe, K.; Bando, M.; Takayama, R.; Ichikawa, J.
    • Journal Title

      J. Fluorine Chem.

      Volume: 171 Pages: 133-138

    • DOI

      10.1016/j.jfluchem.2014.08.013

    • NAID

      120007130272

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Journal Article] Pinpoint-Fluorinated Phenacenes: New Synthesis and Solubility Enhancement Strategies2015

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

      Org. Lett.

      Volume: 17 Issue: 5 Pages: 1126-1129

    • DOI

      10.1021/ol503759d

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Pinpoint-Fluorinated Phenanthrene Synthesis Based on C-F Bond Activation of Difluoroalkenes2015

    • Author(s)
      Fuchibe, K.; Morikawa, T.; Ueda, R.; Okauchi, T.; Ichikawa, J.
    • Journal Title

      J. Fluorine Chem.

      Volume: 179 Pages: 106-115

    • DOI

      10.1016/j.jfluchem.2015.06.008

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Journal Article] Regioselective Synthesis of α,α-Difluorocyclopentanone Derivatives: Domino Nickel-Catalyzed Difluorocyclopropanation/ Ring Expansion Sequence of Silyl Dienol Ethers2015

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

      Org. Lett.

      Volume: 17 Issue: 23 Pages: 5736-5739

    • DOI

      10.1021/acs.orglett.5b02726

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Presentation] パラジウム触媒によるジフルオロアレンの位置選択的スタニル化2018

    • Author(s)
      肥田野友洸、今岡寿仁、渕辺耕平、市川淳士
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 金(I)触媒によるフッ素置換アルキリデンピロリジンの合成:ジフルオロアレンとアジリジンの[2+3]付加環化2018

    • Author(s)
      渕辺耕平、佐近和樹、須藤恭介、市川淳士
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 金(I)触媒を用いるジフルオロアレンとエポキシドの位置選択的[2 + 3]付加環化2017

    • Author(s)
      須藤恭介・渕辺耕平・市川淳士
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大学 日吉キャンパス(神奈川県横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] ジチオエステルのジフルオロメチレン化による硫黄置換ジフルオロアルケンの合成法2017

    • Author(s)
      山田淳史・渕辺耕平・市川淳士
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大学 日吉キャンパス(神奈川県横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] Metal-Catalyzed Regioselective Bond Forming Reactions on Difluoroallenes2017

    • Author(s)
      Fuchibe, K.; Watabe, S.; Abe, M.; Ichikawa, J.
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Method for the Synthesis of Sulfur-substituted Difluoroalkenes via Difluoromethylidenation of Dithioesters2017

    • Author(s)
      Yamada, A.; Takayama, R.; Fuchibe, K.; Ichikawa, J.
    • Organizer
      第8回ハロゲン国際学会
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] トリフルオロメチル置換シクロプロパンにおける選択的なsp3炭素-フッ素結合活性化2016

    • Author(s)
      大木理江・八田響・渕辺耕平・市川淳士
    • Organizer
      第39回フッ素化学討論会
    • Place of Presentation
      アバンセ(佐賀県佐賀市)
    • Year and Date
      2016-09-29
    • Related Report
      2016 Research-status Report
  • [Presentation] α-フルオロシクロペンテノンの位置選択的合成:有機触媒によるジフルオロカルベン生成とフッ素により制御されるナザロフ環化2016

    • Author(s)
      渕辺耕平
    • Organizer
      日本化学会 第96春季年会 コラボレーション企画「未来を創る有機分子触媒」
    • Place of Presentation
      同志社大学 京田辺キャンパス(京都府京田辺市)
    • Year and Date
      2016-03-26
    • Related Report
      2015 Research-status Report
    • Invited
  • [Presentation] ジフルオロアルケンの酸化的カチオン環化と置換PAH合成への応用2016

    • Author(s)
      筥崎智弘・渕辺耕平・市川淳士
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学 京田辺キャンパス(京都府京田辺市)
    • Year and Date
      2016-03-23
    • Related Report
      2015 Research-status Report
  • [Presentation] 不活性なフルオロアレーンの芳香族求核置換反応と芳香環増環サイクルの構築2016

    • Author(s)
      今岡寿仁・渕辺耕平・市川淳士
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学 京田辺キャンパス(京都府京田辺市)
    • Year and Date
      2016-03-23
    • Related Report
      2015 Research-status Report
  • [Presentation] ルイス酸によるトリフルオロメチルシクロプロパンの炭素-フッ素結合活性化 : アレーンのジフルオロホモアリル化2016

    • Author(s)
      大木理江・八田 響・渕辺耕平・市川淳士
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学 京田辺キャンパス(京都府京田辺市)
    • Year and Date
      2016-03-23
    • Related Report
      2015 Research-status Report
  • [Presentation] Catalytic Syntheses of Fluorinated Cyclopentanoids by Difluorocarbene and Its Complexes, Electrophilic Activation of Difluoroallenes: Synthesis and Properties of Pinpoint-Fluorinated PAHs2016

    • Author(s)
      Fuchibe, K.
    • Organizer
      上海有機化学研究所
    • Place of Presentation
      上海(中国)
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] Catalytic Syntheses of Fluorinated Cyclopentanoids by Difluorocarbene and Its Complexes, Electrophilic Activation of Difluoroallenes: Synthesis and Properties of Pinpoint-Fluorinated PAHs2016

    • Author(s)
      Fuchibe, K.
    • Organizer
      華東師範大学
    • Place of Presentation
      上海(中国)
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] Electrophilic Activation of Fluoroalkenes: Synthesis and Properties of Pinpoint-Fluorinated PAHs2016

    • Author(s)
      Fuchibe, K.
    • Organizer
      東華大学
    • Place of Presentation
      上海(中国)
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] Electrophilic Activation of Fluoroalkenes: Synthesis and Properties of Pinpoint-Fluorinated PAHs2016

    • Author(s)
      Fuchibe, K.
    • Organizer
      浙江大学
    • Place of Presentation
      杭州市(中国)
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] Electrophilic Activation of Fluoroalkenes: Synthesis and Properties of Pinpoint-Fluorinated PAHs2016

    • Author(s)
      Fuchibe, K.
    • Organizer
      浙江工業大学
    • Place of Presentation
      杭州市(中国)
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] Control of Difluorocarbene Generation by Organocatalyst and Its Applications2015

    • Author(s)
      Fuchibe, K.; Koseki,Y.; Aono, T.; Bando, M.; Takayama, R.; Ichikawa, J.
    • Organizer
      The 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem)
    • Place of Presentation
      Hawaii Convention Center (U.S.A.)
    • Year and Date
      2015-12-16
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Catalytic Introduction of Difluoromethyl and Difluoromethylene Groups with Difluorocarbene and Its Complexes2015

    • Author(s)
      Fuchibe, K.; Aono, T.; Hu, J.; Takayama, R.; Koseki, Y.; Bando, M.; Ichikawa, J.
    • Organizer
      The 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem)
    • Place of Presentation
      Hawaii Convention Center (U.S.A.)
    • Year and Date
      2015-12-15
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] ルイス酸による炭素-フッ素結合活性化を活用した置換テトラセン合成2015

    • Author(s)
      筥崎智弘・三浦恵祐・北川 翼・渕辺耕平・市川淳士
    • Organizer
      第38回フッ素化学討論会
    • Place of Presentation
      中央区立日本橋公会堂 (東京都中央区)
    • Year and Date
      2015-09-17
    • Related Report
      2015 Research-status Report
  • [Presentation] 遷移金属触媒による位置選択的ジフルオロメチレン挿入法:ジフルオロシクロペンタノン誘導体の合成2015

    • Author(s)
      青野竜也・胡極・篠川恒・渕辺耕平・市川淳士
    • Organizer
      第62回有機金属化学討論会
    • Place of Presentation
      関西大学千里山キャンパス (大阪府吹田市)
    • Year and Date
      2015-09-07
    • Related Report
      2015 Research-status Report
  • [Presentation] 1,1-Difluoroallenes as Synthetic Platforms: Indium-Catalyzed Dimino Synthesis of Pinpoint-Fluorinated PAHs2015

    • Author(s)
      Fuchibe, K.
    • Organizer
      The 6th Japanese-Sino Symposium on Organic Chemistry for Young Scientists
    • Place of Presentation
      秋保リゾートホテル クレセント (宮城県仙台市)
    • Year and Date
      2015-09-06
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Organocatalytic Generation of Difluorocarbene: Synthesis of Difluoromethy1 Thioimidates2015

    • Author(s)
      Fuchibe, K.; Bando, M.; Takayama, R.; Ichikawa, J.
    • Organizer
      第39回 内藤コンファレンス
    • Place of Presentation
      シャトレーゼガトーキングダムサッポロ (北海道札幌市)
    • Year and Date
      2015-07-06
    • Related Report
      2015 Research-status Report
  • [Presentation] ジフルオロアレンのドミノ反応を利用するフッ素置換多環式芳香族炭化水素の合成2015

    • Author(s)
      渕辺耕平・真弓夕佳・趙男・横田実咲・市川淳士
    • Organizer
      第107回 有機合成シンポジウム
    • Place of Presentation
      慶応義塾大学薬学部マルチメディア講堂 (東京都港区)
    • Year and Date
      2015-06-09
    • Related Report
      2015 Research-status Report
  • [Presentation] 有機分子触媒によるジフルオロカルベンの発生制御と合成化学的利用2015

    • Author(s)
      渕辺耕平
    • Organizer
      第8回 有機触媒シンポジウム
    • Place of Presentation
      沖縄県市町村自治会館 自治会館ホール (沖縄県那覇市)
    • Year and Date
      2015-05-10
    • Related Report
      2015 Research-status Report
    • Invited
  • [Presentation] プロトンスポンジ触媒によるジフルオロカルベンの発生と含フッ素シクロペンテノン合成への応用2015

    • Author(s)
      髙山亮・渕辺耕平・市川淳士
    • Organizer
      第8回 有機触媒シンポジウム
    • Place of Presentation
      沖縄県市町村自治会館 自治会館ホール (沖縄県那覇市)
    • Year and Date
      2015-05-10
    • Related Report
      2015 Research-status Report
  • [Book] 有機分子触媒の開発と工業利用2018

    • Author(s)
      渕辺耕平, 市川淳士
    • Total Pages
      12
    • Publisher
      シーエムシー出版
    • ISBN
      9784781313238
    • Related Report
      2017 Annual Research Report
  • [Book] フッ素化学入門2015 - フッ素化合物の合成法2015

    • Author(s)
      市川淳士・渕辺耕平・藤田健志
    • Total Pages
      20
    • Publisher
      三共出版
    • Related Report
      2015 Research-status Report
  • [Remarks] 筑波大学市川淳士研究室ウェブサイト

    • URL

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

    • Related Report
      2016 Research-status Report

URL: 

Published: 2015-04-16   Modified: 2019-10-18  

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