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Development of Selective Oxidation Catalyst by Control of Multi-Nuclear Active Site of Transition Metal and Reaction Field

Research Project

Project/Area Number 18065002
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionThe University of Tokyo

Principal Investigator

MIZUNO Noritaka  The University of Tokyo, 大学院・工学系研究科, 教授 (50181904)

Co-Investigator(Kenkyū-buntansha) YAMAGUCHI Kazuya  東京大学, 大学院・工学系研究科, 講師 (50334313)
KAMADA Keigo  東京大学, 大学院・工学系研究科, 助教 (40451801)
Project Period (FY) 2006 – 2009
Project Status Completed (Fiscal Year 2009)
Budget Amount *help
¥69,600,000 (Direct Cost: ¥69,600,000)
Fiscal Year 2009: ¥10,400,000 (Direct Cost: ¥10,400,000)
Fiscal Year 2008: ¥10,400,000 (Direct Cost: ¥10,400,000)
Fiscal Year 2007: ¥38,400,000 (Direct Cost: ¥38,400,000)
Fiscal Year 2006: ¥10,400,000 (Direct Cost: ¥10,400,000)
Keywords多核遷移金属活性点 / 反応場 / 選択酸化 / 触媒 / 多核金属活性点 / ポリオキソメタレート / 銅 / 多核活性点 / アルキン / 酸化的ホモカップリング / オレフィン / エポキシド / エポキシ化反応 / バナジウム / 過酸化水素 / 固定化触媒
Research Abstract

We have developed the efficient oxidation catalysts such as the divacant lacunary polyoxotungstates and divanadium-substituted polyoxotungstate. The multi-nuclear active sites can activate H_2O_2 and substrates efficiently, resulting in the high catalytic performance for the epoxidation of olefins and Bayer-Villiger oxidation with H_2O_2. The novel selenium-containing dinuclear tungsten species shows the highest catalytic activity for H_2O_2-based epoxidation of homoallylic and allylic alcohols among selenium and tungsten complexes. The stabilization of the transition-state by the hydrogen bonding results in the high reactivity. We have also developed the dicopper-substituted γ-Keggin silicotungstate that can act as an effective homogeneous catalyst for the oxidative homocoupling of alkynes and regioselective 1,3-dipolar cycloaddition of organic azides to alkynes. The cooperative involvement of two copper centers in catalyzing the present reactions has been proposed.

Report

(6 results)
  • 2009 Annual Research Report   Final Research Report ( PDF )
  • 2008 Annual Research Report   Self-evaluation Report ( PDF )
  • 2007 Annual Research Report
  • 2006 Annual Research Report
  • Research Products

    (57 results)

All 2009 2008 2007 2006 Other

All Journal Article (34 results) (of which Peer Reviewed: 9 results) Presentation (16 results) Book (6 results) Remarks (1 results)

  • [Journal Article]2009

    • Author(s)
      Fang, X.; Kogerler, P.; Isaacs, L.; Uchida, S.; Mizuno, N.
    • Journal Title

      J. Am. Chem. Soc. 131

      Pages: 432-433

    • Related Report
      2009 Final Research Report
  • [Journal Article]2009

    • Author(s)
      Kamata, K.; Hirano, T.; Kuzuya, S.; Mizuno, N.
    • Journal Title

      J. Am. Chem. Soc. 131

      Pages: 6997-7004

    • Related Report
      2009 Final Research Report
  • [Journal Article]2009

    • Author(s)
      Tagami, H.; Uchida, S.; Mizuno, N.
    • Journal Title

      Angew. Chem. Int. Ed. 48

      Pages: 6160-6165

    • Related Report
      2009 Final Research Report
  • [Journal Article]2009

    • Author(s)
      Oishi, T.; Yamaguchi, K.; Mizuno, N.
    • Journal Title

      Angew. Chem. Int. Ed. 48

      Pages: 6286-6288

    • Related Report
      2009 Final Research Report
  • [Journal Article]2009

    • Author(s)
      Yoshida, A.; Nakagawa, Y.; Uehara, K.; Hikichi, S.; Mizuno, N.
    • Journal Title

      Angew. Chem. Int. Ed. 48

      Pages: 7055-7058

    • Related Report
      2009 Final Research Report
  • [Journal Article]2009

    • Author(s)
      Bu, W.; Uchida, S.; Mizuno, N.
    • Journal Title

      Angew. Chem. Int. Ed. 48

      Pages: 8281-8284

    • Related Report
      2009 Final Research Report
  • [Journal Article]2009

    • Author(s)
      Ishimoto, R.; Kamata, K.; Mizuno, N.
    • Journal Title

      Angew. Chem. Int. Ed. 48

      Pages: 8900-8904

    • Related Report
      2009 Final Research Report
  • [Journal Article]2009

    • Author(s)
      He, J.; Kim, J.W.; Yamaguchi, K.; Mizuno, N.
    • Journal Title

      Angew. Chem. Int. Ed. 48

      Pages: 9888-9891

    • Related Report
      2009 Final Research Report
  • [Journal Article] Highly Selective Oxidation of Organosilanes to Silanols with Hydrogen Peroxide Catalyzed by Lacunary Polyoxotungstate2009

    • Author(s)
      Ryo Ishimoto, Keigo Kamata, Noritaka Mizuno
    • Journal Title

      Angewandte Chemie International Edition 48

      Pages: 8900-8904

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Micelles and Vesicles Formed by Polyoxometalate-Block Copolymer Composites2009

    • Author(s)
      Weifeng Bu, Sayaka Uchida, Noritaka Mizuno
    • Journal Title

      Angewandte Chemie International Edition 48

      Pages: 8281-8284

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Efficient Catalytic Synthesis of Tertiary and Secondary Amines from Alcohols and Urea2009

    • Author(s)
      Jinling He, Jun won Kim, Kazuya Yamaguchi, Noritaka Mizuno
    • Journal Title

      Angewandte Chemie International Edition 48

      Pages: 9888-9891

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article]2008

    • Author(s)
      Kikukawa, Y.; Yamaguchi, S.; Tsuchida, K.; Nakagawa, Y.; Uehara, K.; Yamaguchi, K.; Mizuno, N.
    • Journal Title

      J. Am. Chem. Soc. 130

      Pages: 5472-5478

    • Related Report
      2009 Final Research Report
  • [Journal Article]2008

    • Author(s)
      Uchida, S.; Kawamoto, R.; Tagami, H.; Nakagawa, Y.; Mizuno, N.
    • Journal Title

      J. Am. Chem. Soc. 130

      Pages: 12370-12376

    • Related Report
      2009 Final Research Report
  • [Journal Article]2008

    • Author(s)
      Kamata, K.; Nakagawa, Y.; Yamaguchi, K.; Mizuno, N.
    • Journal Title

      J. Am. Chem. Soc. 130

      Pages: 15304-15310

    • Related Report
      2009 Final Research Report
  • [Journal Article]2008

    • Author(s)
      Kikukawa, Y.; Yamaguchi, S.; Nakagawa, Y.; Uehara, K.; Uchida, S.; Yamaguchi, K.; Mizuno, N.
    • Journal Title

      J. Am. Chem. Soc. 130

      Pages: 15872-15878

    • Related Report
      2009 Final Research Report
  • [Journal Article]2008

    • Author(s)
      Kim, J.W.; Yamaguchi, K.; Mizuno, N.
    • Journal Title

      Angew. Chem. Int. Ed. 47

      Pages: 9249-9251

    • Related Report
      2009 Final Research Report
  • [Journal Article] 1,3-Dipolar Cycloaddition of Organic Azides to Alkynes by a Dicopper-Substituted Silicotungstate2008

    • Author(s)
      K. Kamata, Y. Nakagawa, K. Yamaguchi, N. Mizuno
    • Journal Title

      J. Am. Chem. Soc 130

      Pages: 15304-15310

    • Related Report
      2008 Self-evaluation Report
  • [Journal Article] Synthesis of a Dialuminum-Substituted Silicotungstate and the Diastereoselective Cyclization of Citronellal Derivatives2008

    • Author(s)
      Y. Kikukawa, S. Yamaguchi, Y. Nakagawa, K. Uehara, S. Uchida, K. Yamaguchi, N. Mizuno
    • Journal Title

      J. Am. Chem. Soc. 130

      Pages: 15872-15878

    • Related Report
      2008 Self-evaluation Report
  • [Journal Article] 1, 3-Dipolar Cycloaddition of Organic Azides to Alkynes by a Dicopper-Substituted Silicotungstate2008

    • Author(s)
      K. Kamata, Y. Nakagawa, K. Yamaguchi, N. Mizuno
    • Journal Title

      Journal of the American Chemical Society 130

      Pages: 15304-15310

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and structural characterization of a monomeric di-copper-substituted silicotungstat[Y-H_2SiW_<10>O_<36>Cu_2(μ-1, 1-N_3)_2]^<4-> and the catalysis of oxidative homocoupling of alkynes2008

    • Author(s)
      K. Yamaguchi, K. Kamata, S. Yamaguchi, M. Kotani, N. Mizuno
    • Journal Title

      Journal of Catalysis 258

      Pages: 121-130

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of a Dialuminum-Substituted Silicotungstate and the Diastereoselective Cyclization of Citronellal Derivatives2008

    • Author(s)
      Y. Kikukawa, S. Yamaguchi, Y. Nakagawa, K. Uehara, S. Uchida, K. Yamaguchi, N. Mizuno
    • Journal Title

      Journal of the American Chemical Society 130

      Pages: 15872-15878

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Efficient Oxidative Alkyne-Alkyne Homocoupling by a Monomeric Dicopper-Substituted Silicotungstate2008

    • Author(s)
      K. Kamata, S. Yamaguchi, M. Kotani, K. Yamaguchi, N. Mizuno
    • Journal Title

      Angewandte Chemie International Edition 47

      Pages: 2407-2410

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article]2007

    • Author(s)
      Okamoto, K.; Uchida, S.; Ito, T.; Mizuno, N.
    • Journal Title

      J. Am. Chem. Soc. 129

      Pages: 7378-7384

    • Related Report
      2009 Final Research Report
  • [Journal Article]2007

    • Author(s)
      Fujiwara, H.; Ogasawara, Y.; Yamaguchi, K.; Mizuno, N.
    • Journal Title

      Angew. Chem. Int. Ed. 46

      Pages: 5202-5204

    • Related Report
      2009 Final Research Report
  • [Journal Article] Self-Organization ofAll-Inorganic Dodecatungstophosphate Nanocrystallites2007

    • Author(s)
      K. Okamoto, S. Uchida T. Ito, N. Mizuno
    • Journal Title

      Journal of the American Chemical Society 129

      Pages: 7378-7384

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A One-Pot Synthesis of Primary Amides from Aldoximes or Aldehydes in Water in the Presence of a Supported Rhodium Catalyst2007

    • Author(s)
      H. Fujiwara, Y. Ogasawara, K. aguchi, N. Mizuno
    • Journal Title

      Angewandte Chemie International Edition 46

      Pages: 5202-5205

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Olefin Epoxidation with Hydrogen Peroxide Catalyzed by Lacunary Polyoxometalate [γ-SiW_(10)O_(34)(H_2O)_2]^<4->2007

    • Author(s)
      K.Kamata, M.Kotani, K.Yamaguchi, S.Hikichi, N.Mizuno
    • Journal Title

      Chem. Eur. J. 13

      Pages: 639-648

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Mechanism of [γ-H_2SiV_2W_(10)O_(40)]^<4->-Catalyzed Epoxidation of Alkenes with Hydrogen Peroxide2007

    • Author(s)
      Y.Nakagawa, N.Mizuno
    • Journal Title

      Inorg. Chem. 46

      Pages: 1727-1736

    • Related Report
      2006 Annual Research Report
  • [Journal Article]2006

    • Author(s)
      Jiang, C.; Lesbani, A.; Kawamoto, R.; Uchida, S.; Mizuno, N.
    • Journal Title

      J. Am. Chem. Soc. 128

      Pages: 14240-14241

    • Related Report
      2009 Final Research Report
  • [Journal Article]2006

    • Author(s)
      Yoshida, A.; Yoshimura, M.; Uehara, K.; Hikichi, S.; Mizuno, N.
    • Journal Title

      Angew. Chem. Int. Ed. 45

      Pages: 1956-1960

    • Related Report
      2009 Final Research Report
  • [Journal Article] An Immobilized Organocatalyst for Cyanosilylation and Epoxidation2006

    • Author(s)
      K.Yamaguchi, T.Imago, Y.Ogasawara, J.Kasai, M.Kotani, N.Mizuno
    • Journal Title

      Adv. Synth. Catal. 348

      Pages: 1516-1520

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Ruthenium hydroxide on magnetite as a magnetically separable heterogeneous catalyst for liquid-phase oxidation and reduction2006

    • Author(s)
      M.Kotani, T.Koike, K.Yamaguchi, N.Mizuno
    • Journal Title

      Green Chem 6

      Pages: 735-741

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Channel-Selective Independent Sorption and Collection of Hydrophilic and Hydrophobic Molecules by Cs_2[Cr_3O(OOCC_2H_5)_6(H_2O)_3]_2[α-SiW_<12>O_<40>] Ionic Crvstal2006

    • Author(s)
      C.Jiang, A.Lesbani, R Kawamoto, S.Uchida, N.Mizuno
    • Journal Title

      J. Am. Chem. Soc. 128

      Pages: 14240-14241

    • Related Report
      2006 Annual Research Report
  • [Journal Article] [γ-1,2-H_2SiV_2W_<10>O_<40>] Immobilized on Surface modified Si0_2 as a Heterogeneous Catalyst for Liquid-phase Oxidation with H_2O_22006

    • Author(s)
      J.Kasai, Y.Nakagawa, S.Uchida, K.Yamaguchi, N.Mizuno
    • Journal Title

      Chem. Eur. J. 12

      Pages: 4176-4184

    • Related Report
      2006 Annual Research Report
  • [Presentation] Green Oxidation Reactions by Polyoxometalate-Based Catalysts : From Molecular to Solid Catalysts2009

    • Author(s)
      Noritaka Mizuno
    • Organizer
      International Symposium on Relations between Homogeneous and Heterogeneous Catalysis XIV
    • Place of Presentation
      Stockholm Sweden
    • Year and Date
      2009-09-17
    • Related Report
      2009 Annual Research Report
  • [Presentation] An Efficient Oxidative Alkyne-Alkyne Homocoupling by a Dicopper-Substituted Silicotungstate2009

    • Organizer
      6th World Congress on Oxidation Catalysis
    • Place of Presentation
      Lille
    • Related Report
      2009 Final Research Report
  • [Presentation] Green Oxidation Reactions by Polyoxometalate-Based Catalysts : From Molecular to Solid Catalysts2009

    • Organizer
      International Symposium on Relations between Homogeneous and Heterogeneous Catalysis XIV
    • Place of Presentation
      Stockholm
    • Related Report
      2009 Final Research Report
  • [Presentation] Design of Selective Oxidation Catalysts with Polyoxometalates2008

    • Author(s)
      Noritaka Mizuno
    • Organizer
      8th International Symposium on Fine Chemistry and Functional Polymers 4th IUPAC International Symposium on Novel Materials and their Synthesis
    • Place of Presentation
      Zhen Jiang
    • Year and Date
      2008-10-15
    • Related Report
      2008 Self-evaluation Report
  • [Presentation] Design of Selective Oxidation Catalysts with Polyoxometalates2008

    • Author(s)
      Noritaka Mizuno
    • Organizer
      18th International Symposium on Fine Chemistry and Functional Polymers (FCFP-XVIII) & 4th IUPAC International Symposium on Novel Materials and their Synthesis(NMS-IV)
    • Place of Presentation
      Best Western Zhenjiang International Hotel
    • Year and Date
      2008-10-01
    • Related Report
      2008 Annual Research Report
  • [Presentation] 構造・粒子形態制御によるナノ構造触媒の創製2008

    • Author(s)
      水野哲孝
    • Organizer
      第102回触媒反応討論会
    • Place of Presentation
      名古屋
    • Year and Date
      2008-09-25
    • Related Report
      2008 Self-evaluation Report
  • [Presentation] Design of Selective Oxidation Catalysts with Polyoxometalates2008

    • Organizer
      18th International Symposium on Fine Chemistry and Functional Polymers 4th IUPAC International Symposium on Novel Materials and their Synthesis
    • Place of Presentation
      ZhenJiang
    • Related Report
      2009 Final Research Report
  • [Presentation] Efficient Functional Group Transformations Heterogeneously Catalyzed by Supported Metal Hydroxides2008

    • Organizer
      11th International Symposium on Natural Product Chemistry
    • Place of Presentation
      Karachi
    • Related Report
      2009 Final Research Report
  • [Presentation] Selective Epoxidation with Hydrogen Peroxide Catalyzed by Polyoxometalate2007

    • Author(s)
      Noritaka Mizuno
    • Organizer
      The 234th National ACS meeting
    • Place of Presentation
      Boston
    • Year and Date
      2007-08-19
    • Related Report
      2007 Annual Research Report
  • [Presentation] Fine Control of Structures and Functions of Polyoxometalates and the Application to Catalyses2007

    • Organizer
      The 21st Century COE-RCMS International Conference on Elucidation and Creation of Molecular Functions
    • Place of Presentation
      Nagoya
    • Related Report
      2009 Final Research Report
  • [Presentation] Selective Epoxidation with Hydrogen Peroxide Catalyzed by Polyoxometalate, Mechanism in Homogeneous and Heterogeneous Catalytic Epoxidation Symposium, the Petroleum Division2007

    • Organizer
      the 234th National ACS Meeting
    • Place of Presentation
      Boston
    • Related Report
      2009 Final Research Report
  • [Presentation] Selective Aerobic Oxidations by Supported Ruthenium Hydroxide Catalysts2007

    • Organizer
      The 11th Korea-Japan Symposium on Catalysis
    • Place of Presentation
      Seoul
    • Related Report
      2009 Final Research Report
  • [Presentation] Selective Oxidation Catalyzed by Polyoxometalate2007

    • Organizer
      Joint Conference of 1st International Conference on Science and Technology for Advanced Ceramics (STAC) & 2nd International Conference on Joining Technology for New Metallic Glasses and Inorganic Materials (JTMC)
    • Place of Presentation
      Kanagawa
    • Related Report
      2009 Final Research Report
  • [Presentation] Design of Selective Oxidation Catalysts with Polyoxometalates2007

    • Organizer
      First International Mini-Symposium on Concerto Catalysis
    • Place of Presentation
      Tokyo
    • Related Report
      2009 Final Research Report
  • [Presentation] Selective Epoxidation of Alkenes with Hydrogen Peroxide Catalyzed by [γ-1, 2-H2SiV2W10O40]4-2006

    • Organizer
      5th International Symposium on Chemistry and Biological Chemistry
    • Place of Presentation
      San Francisco
    • Related Report
      2009 Final Research Report
  • [Presentation] Selective Oxidation with Hydrogen Peroxide Catalyzed by Polyoxometalate2006

    • Organizer
      ISCIC-6 & ISCOC-9
    • Place of Presentation
      Singapore
    • Related Report
      2009 Final Research Report
  • [Book] Liquid-Phase Oxidations with Hydrogen Peroxide and Molecular Oxygen Catalyzed by Polyoxometalate-Based Compounds(ed. by N. Mizuno, Modern Heterogeneous Oxidation Catalysis)2009

    • Author(s)
      Mizuno, N.; Kamata, K.; Uchida, S.; Yamaguchi, K.
    • Publisher
      Wiley-VCH
    • Related Report
      2009 Final Research Report
  • [Book] 錯体化学選書7「超分子錯体」(藤田誠、塩谷光彦 監修)2009

    • Author(s)
      内田さやか, 水野哲孝
    • Publisher
      三共出版
    • Related Report
      2009 Annual Research Report
  • [Book] Liquid-Phase Oxidations with Hydrogen Peroxide and Molecular Oxygen Catalyzed by Polyoxometalate-Based Compounds, Modern Heterogeneous Oxidation Catalysis(ed. by N. Mizuno)2009

    • Author(s)
      N. Mizuno, K. Kamata, S. Uchida, K. Yamaguchi
    • Publisher
      Wiley-VCH
    • Related Report
      2008 Self-evaluation Report
  • [Book] "Activation of Hydrogen Peroxide by Polyoxometalates" in Mechanisms in Homogeneous and Heterogeneous Epoxidation Catalysis(Ed. : S.T.Oyama)2008

    • Author(s)
      N. Mizuno, K. Yamaguchi, K. Kamata, Y. Nakagawa
    • Publisher
      Elsevier
    • Related Report
      2008 Annual Research Report
  • [Book] 環境調和型新材料シリーズ 触媒材料2007

    • Author(s)
      水野哲孝, 鎌田慶吾
    • Publisher
      日刊工業新聞社
    • Related Report
      2007 Annual Research Report
  • [Book] Liquid Phase Oxidation Catalyzed by Polyoxometalates (Surface and Nanomolecular Catalysis(分担執筆))2006

    • Author(s)
      N.Mizuno, K.Kamata, K.Yamaguchi
    • Total Pages
      30
    • Publisher
      Taylor and Francis Group, LLC.
    • Related Report
      2006 Annual Research Report
  • [Remarks] ホームページ等

    • URL

      http://park.itc.u-tokyo.ac.jp/mizuno/

    • Related Report
      2009 Final Research Report

URL: 

Published: 2006-04-01   Modified: 2018-03-28  

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