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Development of Heterogeneous Metal Catalysts for Selective Oxidation and C-H Functionalization using Molecular Oxygen

Research Project

Project/Area Number 25810108
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Green/Environmental chemistry
Research InstitutionTokyo Metropolitan University (2014)
Kyushu University (2013)

Principal Investigator

ISHIDA Tamao  首都大学東京, 都市環境科学研究科, 特任教授 (90444942)

Project Period (FY) 2013-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2014: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2013: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Keywords金属ナノ粒子 / C-H官能基化 / カップリング / 金属酸化物 / 金ナノ粒子触媒 / 金触媒 / C-H活性化 / 固体触媒 / アンモ酸化 / ビアリール
Outline of Final Research Achievements

Zirconia supported palladium hydroxide showed the highest catalytic activity for intramolecular C-H/C-H coupling of diphenylamine to carbazole.
In contrast, cobalt oxide and zirconia supported gold nanoparticle catalysts exhibited the highest catalytic activity for intermolecular C-H/C-H coupling of dimethyl phthalate to give the corresponding biaryl dimers using molecular oxygen as a sole oxidant. Gold catalysts also showed excellent regioselectivity to the symmetrical biaryl derivatives without the addition of ligands and co-catalysts. Substrate scope and kinetic studies revealed that the oxidative coupling proceeded via a nucleophilic aromatic substitution reaction. Gold nanoparticles act not only as catalytic active species but also as bulky ligands to control the regioselectivity of products.
For ammoximation of cycloalkanones using ammonia and molecular oxygen, titania supported gold catalysts showed the highest catalytic activity to give the corresponding cycloalkanoneoximes.

Report

(3 results)
  • 2014 Annual Research Report   Final Research Report ( PDF )
  • 2013 Research-status Report
  • Research Products

    (30 results)

All 2015 2014 2013 Other

All Journal Article (11 results) (of which Peer Reviewed: 11 results,  Acknowledgement Compliant: 1 results) Presentation (16 results) (of which Invited: 2 results) Patent(Industrial Property Rights) (3 results)

  • [Journal Article] Direct C-H Arene Homocoupling over Gold Nanoparticles Supported on Metal Oxides2015

    • Author(s)
      T. Ishida, S. Aikawa, Y. Mise, R. Akebi, A. Hamasaki, T. Honma, H. Ohashi, T. Tsuji, Y. Yamamoto, M. Miyasaka, T. Yokoyama, M. Tokunaga
    • Journal Title

      ChemSusChem

      Volume: 8 Issue: 4 Pages: 695-701

    • DOI

      10.1002/cssc.201402822

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Ethanol Oxidation in Water Catalyzed by Gold Nanoparticles Supported on NiO doped with Cu2015

    • Author(s)
      T. Takei, J. Suenaga, T. Ishida, M. Haruta
    • Journal Title

      Top. Catal.

      Volume: 58 Issue: 4-6 Pages: 295-301

    • DOI

      10.1007/s11244-015-0370-4

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Aerobic oxidation of cyclohexanones to phenols and aryl ethers over supported Pd catalysts2015

    • Author(s)
      Z. Zhang, T. Hashiguchi, T. Ishida, A. Hamasaki, T. Honma, H. Ohashi, T. Yokoyama, M. Tokunaga
    • Journal Title

      Org. Chem. Front.

      Volume: 2 Issue: 6 Pages: 654-660

    • DOI

      10.1039/c4qo00354c

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Formation of Gold Clusters on LaNi Mixed Oxides and Its Catalytic Performance for Isomerization of Allylic Alcohols to Saturated Aldehydes2014

    • Author(s)
      Ishida, T.; Aimoto, J.; Hamasaki, A.; Ohashi, H.; Honma, T.; Yokoyama, T.;Sakata, K.; Okumura,M.; Tokunaga, M.
    • Journal Title

      Chem. Lett.

      Volume: 43 Issue: 8 Pages: 1368-1370

    • DOI

      10.1246/cl.140369

    • NAID

      130004677581

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Preparation of microporous polymer-encapsulated Pd nanoparticles and their catalytic performance for hydrogenation and oxidation2014

    • Author(s)
      Ishida, T.; Onuma, Y.; Kinjo, K.; Hamasaki, A.; Ohashi, H.; Honma, T.; Akita, T.; Yokoyama, T.; Tokunaga, M.; Haruta, M.
    • Journal Title

      Tetrahedron

      Volume: 70 Issue: 36 Pages: 6150-6155

    • DOI

      10.1016/j.tet.2014.04.049

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Homogeneous Pd-Catalyzed Transformation of Terminal Alkenes into Primary Allylic Alcohols and Derivatives2014

    • Author(s)
      R. Tomita, K. Mantani, A. Hamasaki, T. Ishida, M. Tokunaga
    • Journal Title

      Chem. Eur. J.

      Volume: 20 Issue: 32 Pages: 9914-9917

    • DOI

      10.1002/chem.201403373

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Theoretical investigation for isomerization of allylic alcohols over Au6 cluster2014

    • Author(s)
      K. Sakata, H. Koga, T. Ishida, J. Aimoto, M. Tokunaga, M. Okumura
    • Journal Title

      Gold Bull.

      Volume: なし

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Supported palladium hydroxide-catalyzed intramolecular double C–H bond functionalization for synthesis of carbazoles and dibenzofurans2014

    • Author(s)
      Ishida, T.; Tsunoda, R.; Zhang, Z.; Hamasaki, A.; Honma, T.; Ohashi, H.; Yokoyama, T.; Tokunaga, M.
    • Journal Title

      Appl. Catal. B Envir

      Volume: 150-151 Pages: 523-531

    • DOI

      10.1016/j.apcatb.2013.12.051

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Cooperative Catalysis of Palladium Nanoparticles and Cobalt Oxide Support for Formylation of Aryl Iodides under Syngas Atmosphere2014

    • Author(s)
      Hamasaki, A.; Yasutake, Y.; Norio, T.; Ishida, T.; Akita, T.; Ohashi, H.; Yokoyama, T.; Honma, T.; Tokunaga, M
    • Journal Title

      Appl. Catal. A Gen

      Volume: 469 Pages: 146-152

    • DOI

      10.1016/j.apcata.2013.09.043

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Gold Nanoparticles Assisted Formation of Cobalt Species for Intermolecular Hydroaminomethylation and Intramolecular Cyclocarbonylation of Olefins2013

    • Author(s)
      Liu, X.; Hamasaki, A.; Yamane, Y.; Aikawa, S.; Ishida, T.; Haruta, M.; Tokunaga, M
    • Journal Title

      Catal. Sci. Tech

      Volume: 3 Issue: 11 Pages: 3000-3006

    • DOI

      10.1039/c3cy00336a

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Promotional effect of Au on reduction of Ni(II) to form Au-Ni alloy catalysts for hydrogenolysis of benzylic alcohols2013

    • Author(s)
      Nishikawa, H.; Kawamoto, D.; Yamamoto, Y.; Ishida, T.; Ohashi, H.; Akita, T.; Honma, T.; Hamasaki, A.; Yokoyama, T.; Tokunaga, M
    • Journal Title

      J. Catal

      Volume: 307 Pages: 254-264

    • DOI

      10.1016/j.jcat.2013.07.027

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Presentation] 酸化物担持金ナノ粒子を用いる芳香族化合物の酸化的カップリング反応とその機構2015

    • Author(s)
      明日亮太、石田玉青、三瀬善之、相川翔平、濱崎昭行、宮坂 充、山本祥史、辻 哲郎、徳永 信
    • Organizer
      日本化学会第95春 季年会
    • Place of Presentation
      日本大学理工学部船橋キャンパス
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] 金ナノ粒子触媒によるシクロアルカノンの液相アンモオキシム化反応2014

    • Author(s)
      平田大地、石田玉青、濱崎昭行、徳永 信
    • Organizer
      第47回酸化反応討論会
    • Place of Presentation
      熊本・市民会館崇城大学ホール
    • Year and Date
      2014-11-14 – 2014-11-15
    • Related Report
      2014 Annual Research Report
  • [Presentation] Direct C-H/C-H Homocoupling Catalyzed by Gold Nanoparticles Supported on Metal Oxides2014

    • Author(s)
      T. Ishida, S. Aikawa, Y. Mise, R. Akebi, A. Hamasaki, T. Honma, H. Ohashi, T. Tsuji, M. Miyasaka, Y. Yamamoto, T. Yokoyama, M. Tokunaga
    • Organizer
      14th Tateshina Conference on Organic Chemistry
    • Place of Presentation
      Teteshina Forum
    • Year and Date
      2014-11-07 – 2014-11-09
    • Related Report
      2014 Annual Research Report
  • [Presentation] 金属酸化物担持金ナノ粒子触媒を用いたC-H 活性化を経るビフェニル化合物の合成2014

    • Author(s)
      三瀬善之、石田玉青・相川翔平・明日亮太・濱﨑昭行・本間徹生・大橋弘範・横山拓史・宮坂 充・山本祥史・辻 哲郎・徳永 信
    • Organizer
      第61回有機金属化学討論会
    • Place of Presentation
      九州大学
    • Year and Date
      2014-09-23 – 2014-09-25
    • Related Report
      2014 Annual Research Report
  • [Presentation] Gold Nanoparticle-Catalyzed C-H Bond Functionalization for Biaryl Synthesis2014

    • Author(s)
      Y. Mise, S. Aikawa, T. Ishida, R. Akebi, A. Hamasaki, H. Ohashi, T. Honma, T. Tsuji, Y. Yamamoto, M. Miyasaka, T. Yokoyama, M. Tokunaga
    • Organizer
      International Symposium on Small Particles and Inorganic Clusters (ISSPIC XVII)
    • Place of Presentation
      Kyushu University
    • Year and Date
      2014-09-07 – 2014-09-12
    • Related Report
      2014 Annual Research Report
  • [Presentation] Clusters on La-Ni Mixed Oxides and its Catalytic Performance for Isomerization of Allylic Alcohols to Saturated Aldehydes2014

    • Author(s)
      T. Ishida, J. Aimoto, A. Hamasaki, H. Ohashi, T. Hon,a, T. Yokoyama, K. Sakata, M. Okumura, M. Tokunaga
    • Organizer
      International Symposium on Small Particles and Inorganic Clusters (ISSPIC XVII)
    • Place of Presentation
      Kyushu University
    • Year and Date
      2014-09-07 – 2014-09-12
    • Related Report
      2014 Annual Research Report
  • [Presentation] 酸化物担持金ナノ粒子触媒 を用いるフタル酸ジメチルの酸化的カップリング反応2014

    • Author(s)
      三瀬善之、相川 翔平・石田玉青・濱崎昭行・宮坂 充・山本祥史・辻 哲郎・徳永 信
    • Organizer
      分子活性化-有機分子触媒合同シンポジウム
    • Place of Presentation
      北海道大学
    • Year and Date
      2014-06-20
    • Related Report
      2014 Annual Research Report
  • [Presentation] Gold-Catalyzed Selective Oxidation in Liquid Phase2014

    • Author(s)
      T. Ishida
    • Organizer
      Kick-Off Workshop for Research Center for Gold Chemistry
    • Place of Presentation
      Tokyo Metropolitan University
    • Year and Date
      2014-05-14 – 2014-05-15
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] 酸化コバルト担持金ナノ粒子触媒を用いたフタル酸ジメチルの酸化的カップリング反応

    • Author(s)
      相川翔平、三瀬喜之、石田玉青、濱崎昭行、宮坂充、山本祥史、辻哲郎、徳永信
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学
    • Related Report
      2013 Research-status Report
  • [Presentation] 金属酸化物担持金ナノ粒子触媒を用いた芳香族化合物の酸化的カップリング反応

    • Author(s)
      三瀬喜之、相川翔平、石田玉青、濱崎昭行、宮坂充、山本祥史、辻哲郎、徳永信
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学
    • Related Report
      2013 Research-status Report
  • [Presentation] 金ナノ粒子触媒によるC-H結合活性化を経るビフェニル化合物の合成

    • Author(s)
      石田玉青、相川翔平、三瀬喜之、濱崎昭行、宮坂充、山本祥史、辻哲郎、
    • Organizer
      第113回触媒討論会
    • Place of Presentation
      ロワジール豊橋
    • Related Report
      2013 Research-status Report
  • [Presentation] 金触媒を用いたシクロアルカノンのアンモオキシム化反応

    • Author(s)
      平田大地、石田玉青、濱崎昭行、徳永信
    • Organizer
      第113回触媒討論会
    • Place of Presentation
      ロワジール豊橋
    • Related Report
      2013 Research-status Report
  • [Presentation] 担持パラジウム触媒を用いたシクロヘキサノンからのアルコキシベンゼンの合成

    • Author(s)
      橋口大真、張振中、石田玉青、濱崎昭行、徳永信
    • Organizer
      第113回触媒討論会
    • Place of Presentation
      ロワジール豊橋
    • Related Report
      2013 Research-status Report
  • [Presentation] 担持パラジウム触媒による液相条件におけるフルフラールの脱カルボニル化

    • Author(s)
      金城浩太、石田玉青、濱崎昭行、井澤雄輔、宇都宮賢、徳永信
    • Organizer
      第113回触媒討論会
    • Place of Presentation
      ロワジール豊橋
    • Related Report
      2013 Research-status Report
  • [Presentation] Aerobic oxidation of cyclohexanones to cyclic enones, phenols, and phenyl ethers over supported palladium catalysts

    • Author(s)
      張振中、橋口大真、石田玉青、濱崎昭行、徳永信
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学
    • Related Report
      2013 Research-status Report
  • [Presentation] Supported palladium hydroxide-catalyzed C-H bond functionalization for synthesis of carbazoles and dibenzofurans

    • Author(s)
      Tamao Ishida
    • Organizer
      21st Joint Seminar of KB-CSJ and BB-KCS
    • Place of Presentation
      韓国・釜慶大学
    • Related Report
      2013 Research-status Report
    • Invited
  • [Patent(Industrial Property Rights)] 飲料中の含硫黄化合物の除去方法2015

    • Inventor(s)
      徳永 信、石田玉青、山本裕典、長谷川貴之、磯谷敦子、藤井 力
    • Industrial Property Rights Holder
      徳永 信、石田玉青、山本裕典、長谷川貴之、磯谷敦子、藤井 力
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2015-037904
    • Filing Date
      2015-02-27
    • Related Report
      2014 Annual Research Report
  • [Patent(Industrial Property Rights)] 後周期遷移金属微粒子担持体の製造方法2015

    • Inventor(s)
      徳永 信、石田玉青、山本裕典、長谷川貴之、他3名
    • Industrial Property Rights Holder
      徳永 信、石田玉青、山本裕典、長谷川貴之、他3名
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2015-037905
    • Filing Date
      2015-02-27
    • Related Report
      2014 Annual Research Report
  • [Patent(Industrial Property Rights)] アリルアルコール類の製造方法2015

    • Inventor(s)
      徳永 信、石田玉青、張 振中、井澤雄輔
    • Industrial Property Rights Holder
      徳永 信、石田玉青、張 振中、井澤雄輔
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2015-025722
    • Filing Date
      2015-02-12
    • Related Report
      2014 Annual Research Report

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Published: 2014-07-25   Modified: 2019-07-29  

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