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

• Project/Area Number: 18065002
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: The 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: ¥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.

Research Products

• [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
• [Journal Article] (2009)
  • Author(s): Kamata, K.; Hirano, T.; Kuzuya, S.; Mizuno, N.
  • Journal Title: J. Am. Chem. Soc. 131 Pages: 6997-7004
• [Journal Article] (2009)
  • Author(s): Tagami, H.; Uchida, S.; Mizuno, N.
  • Journal Title: Angew. Chem. Int. Ed. 48 Pages: 6160-6165
• [Journal Article] (2009)
  • Author(s): Oishi, T.; Yamaguchi, K.; Mizuno, N.
  • Journal Title: Angew. Chem. Int. Ed. 48 Pages: 6286-6288
• [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
• [Journal Article] (2009)
  • Author(s): Bu, W.; Uchida, S.; Mizuno, N.
  • Journal Title: Angew. Chem. Int. Ed. 48 Pages: 8281-8284
• [Journal Article] (2009)
  • Author(s): Ishimoto, R.; Kamata, K.; Mizuno, N.
  • Journal Title: Angew. Chem. Int. Ed. 48 Pages: 8900-8904
• [Journal Article] (2009)
  • Author(s): He, J.; Kim, J.W.; Yamaguchi, K.; Mizuno, N.
  • Journal Title: Angew. Chem. Int. Ed. 48 Pages: 9888-9891
• [Journal Article] Highly Selective Oxidation of Organosilanes to Silanols with Hydrogen Peroxide Catalyzed by Lacunary Polyoxotungstate (2009)
  • Author(s): Ryo Ishimoto, Keigo Kamata, Noritaka Mizuno
  • Journal Title: Angewandte Chemie International Edition 48 Pages: 8900-8904
  • Peer Reviewed
• [Journal Article] Micelles and Vesicles Formed by Polyoxometalate-Block Copolymer Composites (2009)
  • Author(s): Weifeng Bu, Sayaka Uchida, Noritaka Mizuno
  • Journal Title: Angewandte Chemie International Edition 48 Pages: 8281-8284
  • Peer Reviewed
• [Journal Article] Efficient Catalytic Synthesis of Tertiary and Secondary Amines from Alcohols and Urea (2009)
  • Author(s): Jinling He, Jun won Kim, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Angewandte Chemie International Edition 48 Pages: 9888-9891
  • 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
• [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
• [Journal Article] (2008)
  • Author(s): Kamata, K.; Nakagawa, Y.; Yamaguchi, K.; Mizuno, N.
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 15304-15310
• [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
• [Journal Article] (2008)
  • Author(s): Kim, J.W.; Yamaguchi, K.; Mizuno, N.
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 9249-9251
• [Journal Article] 1,3-Dipolar Cycloaddition of Organic Azides to Alkynes by a Dicopper-Substituted Silicotungstate (2008)
  • Author(s): K. Kamata, Y. Nakagawa, K. Yamaguchi, N. Mizuno
  • Journal Title: J. Am. Chem. Soc 130 Pages: 15304-15310
• [Journal Article] Synthesis of a Dialuminum-Substituted Silicotungstate and the Diastereoselective Cyclization of Citronellal Derivatives (2008)
  • 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
• [Journal Article] 1, 3-Dipolar Cycloaddition of Organic Azides to Alkynes by a Dicopper-Substituted Silicotungstate (2008)
  • Author(s): K. Kamata, Y. Nakagawa, K. Yamaguchi, N. Mizuno
  • Journal Title: Journal of the American Chemical Society 130 Pages: 15304-15310
  • 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 alkynes (2008)
  • Author(s): K. Yamaguchi, K. Kamata, S. Yamaguchi, M. Kotani, N. Mizuno
  • Journal Title: Journal of Catalysis 258 Pages: 121-130
  • Peer Reviewed
• [Journal Article] Synthesis of a Dialuminum-Substituted Silicotungstate and the Diastereoselective Cyclization of Citronellal Derivatives (2008)
  • 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
  • Peer Reviewed
• [Journal Article] Efficient Oxidative Alkyne-Alkyne Homocoupling by a Monomeric Dicopper-Substituted Silicotungstate (2008)
  • Author(s): K. Kamata, S. Yamaguchi, M. Kotani, K. Yamaguchi, N. Mizuno
  • Journal Title: Angewandte Chemie International Edition 47 Pages: 2407-2410
  • 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
• [Journal Article] (2007)
  • Author(s): Fujiwara, H.; Ogasawara, Y.; Yamaguchi, K.; Mizuno, N.
  • Journal Title: Angew. Chem. Int. Ed. 46 Pages: 5202-5204
• [Journal Article] Self-Organization ofAll-Inorganic Dodecatungstophosphate Nanocrystallites (2007)
  • Author(s): K. Okamoto, S. Uchida T. Ito, N. Mizuno
  • Journal Title: Journal of the American Chemical Society 129 Pages: 7378-7384
  • Peer Reviewed
• [Journal Article] A One-Pot Synthesis of Primary Amides from Aldoximes or Aldehydes in Water in the Presence of a Supported Rhodium Catalyst (2007)
  • Author(s): H. Fujiwara, Y. Ogasawara, K. aguchi, N. Mizuno
  • Journal Title: Angewandte Chemie International Edition 46 Pages: 5202-5205
  • 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
• [Journal Article] Mechanism of [γ-H_2SiV_2W_(10)O_(40)]^<4->-Catalyzed Epoxidation of Alkenes with Hydrogen Peroxide (2007)
  • Author(s): Y.Nakagawa, N.Mizuno
  • Journal Title: Inorg. Chem. 46 Pages: 1727-1736
• [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
• [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
• [Journal Article] An Immobilized Organocatalyst for Cyanosilylation and Epoxidation (2006)
  • Author(s): K.Yamaguchi, T.Imago, Y.Ogasawara, J.Kasai, M.Kotani, N.Mizuno
  • Journal Title: Adv. Synth. Catal. 348 Pages: 1516-1520
• [Journal Article] Ruthenium hydroxide on magnetite as a magnetically separable heterogeneous catalyst for liquid-phase oxidation and reduction (2006)
  • Author(s): M.Kotani, T.Koike, K.Yamaguchi, N.Mizuno
  • Journal Title: Green Chem 6 Pages: 735-741
• [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 Crvstal (2006)
  • Author(s): C.Jiang, A.Lesbani, R Kawamoto, S.Uchida, N.Mizuno
  • Journal Title: J. Am. Chem. Soc. 128 Pages: 14240-14241
• [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_2 (2006)
  • Author(s): J.Kasai, Y.Nakagawa, S.Uchida, K.Yamaguchi, N.Mizuno
  • Journal Title: Chem. Eur. J. 12 Pages: 4176-4184
• [Presentation] Green Oxidation Reactions by Polyoxometalate-Based Catalysts : From Molecular to Solid Catalysts (2009)
  • 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
• [Presentation] An Efficient Oxidative Alkyne-Alkyne Homocoupling by a Dicopper-Substituted Silicotungstate (2009)
  • Organizer: 6th World Congress on Oxidation Catalysis
  • Place of Presentation: Lille
• [Presentation] Green Oxidation Reactions by Polyoxometalate-Based Catalysts : From Molecular to Solid Catalysts (2009)
  • Organizer: International Symposium on Relations between Homogeneous and Heterogeneous Catalysis XIV
  • Place of Presentation: Stockholm
• [Presentation] Design of Selective Oxidation Catalysts with Polyoxometalates (2008)
  • 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
• [Presentation] Design of Selective Oxidation Catalysts with Polyoxometalates (2008)
  • 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
• [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
• [Presentation] Design of Selective Oxidation Catalysts with Polyoxometalates (2008)
  • Organizer: 18th International Symposium on Fine Chemistry and Functional Polymers 4th IUPAC International Symposium on Novel Materials and their Synthesis
  • Place of Presentation: ZhenJiang
• [Presentation] Efficient Functional Group Transformations Heterogeneously Catalyzed by Supported Metal Hydroxides (2008)
  • Organizer: 11th International Symposium on Natural Product Chemistry
  • Place of Presentation: Karachi
• [Presentation] Selective Epoxidation with Hydrogen Peroxide Catalyzed by Polyoxometalate (2007)
  • Author(s): Noritaka Mizuno
  • Organizer: The 234th National ACS meeting
  • Place of Presentation: Boston
  • Year and Date: 2007-08-19
• [Presentation] Fine Control of Structures and Functions of Polyoxometalates and the Application to Catalyses (2007)
  • Organizer: The 21st Century COE-RCMS International Conference on Elucidation and Creation of Molecular Functions
  • Place of Presentation: Nagoya
• [Presentation] Selective Epoxidation with Hydrogen Peroxide Catalyzed by Polyoxometalate, Mechanism in Homogeneous and Heterogeneous Catalytic Epoxidation Symposium, the Petroleum Division (2007)
  • Organizer: the 234th National ACS Meeting
  • Place of Presentation: Boston
• [Presentation] Selective Aerobic Oxidations by Supported Ruthenium Hydroxide Catalysts (2007)
  • Organizer: The 11th Korea-Japan Symposium on Catalysis
  • Place of Presentation: Seoul
• [Presentation] Selective Oxidation Catalyzed by Polyoxometalate (2007)
  • 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
• [Presentation] Design of Selective Oxidation Catalysts with Polyoxometalates (2007)
  • Organizer: First International Mini-Symposium on Concerto Catalysis
  • Place of Presentation: Tokyo
• [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
• [Presentation] Selective Oxidation with Hydrogen Peroxide Catalyzed by Polyoxometalate (2006)
  • Organizer: ISCIC-6 & ISCOC-9
  • Place of Presentation: Singapore
• [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
• [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
• [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
• [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
• [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
• [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.
• [Remarks] ホームページ等
  • URL: http://park.itc.u-tokyo.ac.jp/mizuno/