• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to project page

2010 Fiscal Year Annual Research Report

ラジカル反応の集積化

Planned Research

Project AreaOrganic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials
Project/Area Number 21106003
Research InstitutionOsaka Prefecture University

Principal Investigator

柳 日馨  大阪府立大学, 理学系研究科, 教授 (80210821)

Co-Investigator(Kenkyū-buntansha) 福山 高英  大阪府立大学, 理学系研究科, 准教授 (60332962)
小林 正治  大阪工業大学, 工学部, 講師 (30374903)
Keywords集積型ラジカル反応 / マルチタスク触媒 / 1,4-ジエン / 位置選択的アリル化 / マイクロフロー系 / C-N結合解裂 / ジフェニルヒドラジル基
Research Abstract

本研究ではわずかなエネルギー供与で優れた選択性と効率性を発現する高効率ラジカル反応系の開拓を反応開発と反応デバイス選択の両面から検討し、その集積化を経て重要な生物活性物質や機能性物質の合成に資する力量ある方法論に高めることを目的としている。本年度では時間および空間集積型の多成分集積反応の開発を、光や熱を効率的に活用する反応を基軸として行なった。ラジカル連鎖反応と触媒的クロスカップリング反応を積極的に組み合わせた合成手法や多段階のラジカル反応の開始段階と終結段階に金属種を効果的に機能させる活性種の集積型反応についてC-H活性化の観点から検討するとともに、熱効率の良いマイクロフロー型反応装置により、リビングラジカル重合反応を試み、ラジカル反応を集積化合成プロセスへと導くための基盤形成も行った。結果、臭素ラジカルをメディエーターとするアレンへの位置選択的ブロモアリル化反応を見出した。また臭化銅(II)を用いた1,3-シクロヘキサンジオン誘導体の連続型臭素化/芳香族化/ラクトン環化法を開発した。これらの反応を続く触媒的なクロスカップリング反応と連結させ、多置換オレフィンや多置換フェノールの形成手法とした。ポリオキソタングステートの光触媒作用を利用し光C-Hカルボニル化反応に基づいた置換ケトンの合成法を開発した。スチレンのリビングラジカル重合反応をマイクロフロー型反応装置により試み、バッチ反応系に対する反応効率の優位性を示した。さらにパラホルムアルデヒドをラジカル反応の合成素子として用い、ヒドロキシメチル化反応が進行することを見出した。

  • Research Products

    (35 results)

All 2011 2010 Other

All Journal Article (14 results) (of which Peer Reviewed: 14 results) Presentation (21 results)

  • [Journal Article] Efficient Iridium-Catalyzed Decarbonylation Reaction of Aliphatic Carboxylic Acids Leading to Internal or Terminal Alkenes2011

    • Author(s)
      Maetani, S.; Fukuyama, T.; Suzuki, N.; Ishihara, D.; Ryu, I.
    • Journal Title

      Organometallics

      Volume: 30 Pages: 1389-1394

    • Peer Reviewed
  • [Journal Article] Atom-Economical Synthesis of Unsymmetrical Ketones through Photocatalyzed CH Activation of Alkanes and Coupling with CO and Electrophilic Alkenes2011

    • Author(s)
      Ryu, I.; Tani, A.; Fukuyama, T.; Ravelli, D., Fagnoni, M., Albini, A.
    • Journal Title

      Angew.Chem.Int.Ed

      Volume: 50 Pages: 1869-1872

    • Peer Reviewed
  • [Journal Article] Microflow photo-radical chlorination of cycloalkanes2011

    • Author(s)
      Matsubara, H.; Hino, Y.; Tokizane, M.; Ryu, I.
    • Journal Title

      Chemical Engineering Journal

      Volume: 167 Pages: 567-571

    • Peer Reviewed
  • [Journal Article] Monolithic and Flexible Polyimide Film Microreactors for Organic Microchemical Applications Fabricated by Laser Ablation2010

    • Author(s)
      Min, K.I.; Lee, T.H.; Park, C.P.; Wu, Z.W.; Girault, H.H.; Ryu, I.; Fukuyama, T.; Mukai, Y.; Kim, D.P.
    • Journal Title

      Angew.Chem.Int.Ed.

      Volume: 49 Pages: 7063-7067

    • Peer Reviewed
  • [Journal Article] Regioselective Synthesis of 1-Bromo-1,4-dienes by Free-Radical-Mediated Bromoallylation of Activated Acetylenes2010

    • Author(s)
      Kippo, T.; Fukuyama, T.; Ryu, I.
    • Journal Title

      Org.Lett.

      Volume: 12 Pages: 4006-4009

    • Peer Reviewed
  • [Journal Article] Diastereoselective [2+2] Photocycloaddition of Chiral Cyclic Enone and Cyclopentene Using a Microflow Reactor System2010

    • Author(s)
      Tsutsumi, K.; Terao, K.; Yamaguchi, H.; Yoshimura, S.; Morimoto, T.; Kakiuchi, K.; Fukuyama, T.; Ryu, I.
    • Journal Title

      Chem.Lett.

      Volume: 39 Pages: 828-829

    • Peer Reviewed
  • [Journal Article] Thermal Retro-Aldol Reaction Using Fluorous Ether F-626 as a Reaction Medium2010

    • Author(s)
      Fukuyama, T.; Kawamoto, T.; Okamura, T.; Denichoux, A.; Ryu, I.
    • Journal Title

      Synlett

      Volume: 14 Pages: 2193-2196

    • Peer Reviewed
  • [Journal Article] A Photoirradiative Phase-Vanishing Method : Efficient Generation of HBr from Alkanes and Molecular Bromine and Its Use for Subsequent Radical Addition to Terminal Alkenes2010

    • Author(s)
      Matsubara, H.; Tsukida, M.; Ishihara, D.; Kuniyoshi, K.; Ryu, I.
    • Journal Title

      Synlett

      Volume: 13 Pages: 2014-2018

    • Peer Reviewed
  • [Journal Article] Synthesis of Functionalized Resorcinols by Rhodium-Catalyzed [5+1] Cycloaddition Reaction of 3-Acyloxy-1,4-Enynes with CO2010

    • Author(s)
      Brancour, C.; Fukuyama, T.; Ohta, Y.; Ryu, I.; Dhimane, A.L.; Fensterbank, L.; Malacria, M.
    • Journal Title

      Chem.Commun.

      Volume: 46 Pages: 5470-5472

    • Peer Reviewed
  • [Journal Article] Synthesis of Alkyl Alkynyl Ketones by Pd/Light-Induced Three-Component Coupling Reactions of Iodoalkanes, CO, and 1-Alkynes2010

    • Author(s)
      Fusano, A.; Fukuyama, T.; Nishitani, S.; Inouye, T.; Ryu, I.
    • Journal Title

      Org.Lett.

      Volume: 12 Pages: 2410-2413

    • Peer Reviewed
  • [Journal Article] Stannylcarbonylation of Hydroxy-substituted Alkynes.Intramoleuclar Trapping of α-Ketenyl Radicals by a Hydroxy Group Leading to Lactols2010

    • Author(s)
      Ryu, I.; Fukuyama, T.; Nobuta, O.; Uenoyama, Y.
    • Journal Title

      Bull.Korean Chem.Soc.

      Volume: 31 Pages: 545-546

    • Peer Reviewed
  • [Journal Article] Synthesis of 2-Hydroxymethyl Ketones by Ruthenium Hydride-Catalyzed Cross-Coupling Reaction of alpha, beta-Unsaturated Aldehydes with Primary Alcohols2010

    • Author(s)
      Denichoux, A.; Fukuyama, T.; Doi, T.; Horiguchi, J.; Ryu, I.
    • Journal Title

      Org.Lett.

      Volume: 12 Pages: 1-3

    • Peer Reviewed
  • [Journal Article] Vicinal C-Functionalization of Alkenes. Pd/Light-Induced Multi-Component Coupling Reactions Leading to 4-Keto Esters and Lactones

    • Author(s)
      Fusano, A.; Sumino, S.; Fukuyama, T.; Ryu, I.
    • Journal Title

      Org.Lett.

      Volume: (in press)

    • Peer Reviewed
  • [Journal Article] Radical Carbonylation of ω-Alkynylamines Leading to α-Methylene lactams. Synthetic Scope and the Mechanistic Insights

    • Author(s)
      Ryu, I.; Fukuyama, T.; Tojino, M.; Uenoyama, Y.; Yonamine, Y.; Terasoma, N.; Matsubara, H.
    • Journal Title

      Org.Biomol.Chem.

      Volume: (in press)

    • Peer Reviewed
  • [Presentation] オキシ-Favorskii転位を用いる双環性置換エーテル化合物の立体選択的構築手法2011

    • Author(s)
      木下達弘・小林正治・片山達矢・和田昌人・益山新樹・柳日馨
    • Organizer
      日本化学会第91春季年会
    • Place of Presentation
      (日本化学会第91春季年会(2011)講演予稿集)
    • Year and Date
      2011-03-11
  • [Presentation] 21世紀の化学製造はフロー系で:巨大プラントとの決別2011

    • Author(s)
      柳日馨
    • Organizer
      大阪府立大学理学部公開セミナー;21世紀における化学のあるべき
    • Place of Presentation
      大阪
    • Year and Date
      2011-01-22
  • [Presentation] Energy-Saving Photoreaction System Using Microreactor and Compact Light Source2010

    • Author(s)
      Fukuyama, T.; Ryu, I.
    • Organizer
      The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      20101215-20101220
  • [Presentation] Continuous Catalyst Recycling System Using Microreactor and Ionic Liquid, and Its Application to 100-Gram Scale Synthesis of Matrix Metalloproteinase Inhibitor's Precursor2010

    • Author(s)
      Fukuyama, T.; Rahman, M.T.; Ryu, I.
    • Organizer
      The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      20101215-20101220
  • [Presentation] One-Pot Synthesis of Substituted 1,4-Dienes via the Consecutive Radical-Mediated Bromoallylation of Alkynes and Pd-catalyzed Cross-Coupling Reactions2010

    • Author(s)
      Kippo, T.; Fukuyama, T.; Ryu, I.
    • Organizer
      The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      20101215-20101220
  • [Presentation] Organocatalytic Enantioselective Synthesis of Nitrogen-Substituted Dihydropyran-2-ones, a Key Synthetic Intermediate of 1β-Methylcarbapenems2010

    • Author(s)
      Kinoshita, T.; Kobayashi, S.; Uehara; H.Sudo, T.; Masuyama, A.; Ryu, I.
    • Organizer
      The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      20101215-20101220
  • [Presentation] Application of a Continuous Microflow System to Radical Multi-Component Reactions2010

    • Author(s)
      Fusano, A.; Fukuyama, T.; Ryu, I.
    • Organizer
      The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      20101215-20101220
  • [Presentation] Pd/light Induced Radical Multi-Component Reactions2010

    • Author(s)
      Fusano, A.; Fukuyama, T.; Ryu, I.
    • Organizer
      The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      20101215-20101220
  • [Presentation] Photocatalytic Radical Carbonylation Reaction at C-H Bond Using Tetrabutylammonium Decatungstate (TBADT)2010

    • Author(s)
      Tani, A.; Fukuyama, T.; Ryu, I.; Fagnoni, M.
    • Organizer
      The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      20101215-20101220
  • [Presentation] Nitroxide-Mediated Radical Polymerization of Methyl Methacrylate Using a Microflow Reactor2010

    • Author(s)
      Kajihara, Y.; Fukuyama, T.; Ryu, I.
    • Organizer
      The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      20101215-20101220
  • [Presentation] Koch-Haaf Reaction Using a Hastelloy-Made Microreactor2010

    • Author(s)
      Mukai, Y.; Fukuyama, T.; Ryu, I.
    • Organizer
      The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      20101215-20101220
  • [Presentation] Oxy-Favorskii Rearrangement as a Tool for the Synthesis of Stereochemically Defined Bicyclic Ethers and Its Application to the Total Synthesis of (±)-Communiol E2010

    • Author(s)
      Kobayashi, S.; Kinoshita, T.; Kawamoto, T.; Masuyama, A.; Ryu, I.
    • Organizer
      The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      20101215-20101220
  • [Presentation] Diastereoselective[2+2]Photocycloaddition of Chiral Cyclic Enone and Cyclopentene Using a Microflow Reactor System2010

    • Author(s)
      Terao, K.; Tsutsumi, K.; Yamaguchi, H.; Yoshimura, S.; Nishiyama, Y.; Morimoto, T.; Kakiuchi, K.; Fukuyama, T.; Ryu, I.
    • Organizer
      The 2010 International Chemical Congress of Pacific Basin Societies (Pacifichem 2010)
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      20101215-20101220
  • [Presentation] Regioselective Synthesis of 1-Bromo-1, 4-Dienes : Radical Bromoallylation of Terminal Acetylenes2010

    • Author(s)
      Kippo, T.; Fukuyama, T.; Ryu, I.
    • Organizer
      The Sixth International Symposium on Integrated Synthesis (ISIS-6)
    • Place of Presentation
      兵庫
    • Year and Date
      20100823-20100824
  • [Presentation] Radical Carbonylation under Atmospheric Pressure of CO. Tin-Free Hydroxymethylation of Alkyl Iodides2010

    • Author(s)
      Kobayashi, S.; Kawamoto, T.; Uehara, S.; Fukuyama, T.; Ryu, I.
    • Organizer
      The Sixth International Symposium on Integrated Synthesis (ISIS-6)
    • Place of Presentation
      兵庫
    • Year and Date
      20100823-20100824
  • [Presentation] Pd/Light Induced Radical Multi-Component Coupling Reactions2010

    • Author(s)
      Fusano, A.; Fukuyama, T.; Sumino, S.; Ryu, I.
    • Organizer
      The Sixth International Symposium on Integrated Synthesis (ISIS-6)
    • Place of Presentation
      兵庫
    • Year and Date
      20100823-20100824
  • [Presentation] Stereoselective Synthesis of the 2-Substituted Bicyclic Ethers through Oxy-Favorskii Rearrangement2010

    • Author(s)
      Kinoshita, T.; Kobayashi, S.; Katayama, T.; Wada, M.; Kawamoto, T.; Masuyama, A.; Ryu, I.
    • Organizer
      The Sixth International Symposium on Integrated Synthesis (ISIS-6)
    • Place of Presentation
      兵庫
    • Year and Date
      20100823-20100824
  • [Presentation] Some Unique Anionic Strategies for Multi-Component Coupling Reactions2010

    • Author(s)
      Ryu, I.
    • Organizer
      9^<th> International Symposium on Carbanion Chemistry
    • Place of Presentation
      Florence, Italy
    • Year and Date
      20100720-20100724
  • [Presentation] Acyl Radicals from Alkanes by a Tandem Photocatalytic C-H Activation/Carbonylation Process.2010

    • Author(s)
      Ryu, I.Tani, A.; Fukuyama, T.; Ravelli, D.; Fagnoni, M.; Albini, A.
    • Organizer
      EUCHEM Conference on Organic Free Radical
    • Place of Presentation
      Bologna, Italy
    • Year and Date
      20100701-20100702
  • [Presentation] マイクロリアクターによる連続フロー型有機合成の進歩2010

    • Author(s)
      柳日馨
    • Organizer
      マイクロ化学プロセス分科会講演会
    • Place of Presentation
      東京
    • Year and Date
      2010-11-26
  • [Presentation] 一酸化炭素を組み込む多成分連結反応の新展開2010

    • Author(s)
      柳日馨
    • Organizer
      第27回有機合成夏期セミナー
    • Place of Presentation
      兵庫
    • Year and Date
      2010-09-02

URL: 

Published: 2012-07-19  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi