Development of Solid Acid and Oxidation Catalysts Based on Metal Hydroxides

• Project/Area Number: 18686064
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Catalyst/Resource chemical process
• Research Institution: The University of Tokyo
• Principal Investigator: YAMAGUCHI Kazuya The University of Tokyo, 工学系研究科 (50334313)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥28,600,000 (Direct Cost: ¥22,000,000、Indirect Cost: ¥6,600,000); Fiscal Year 2008: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2007: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2006: ¥19,760,000 (Direct Cost: ¥15,200,000、Indirect Cost: ¥4,560,000)
• Keywords: 金属水酸化物 / 不均一系触媒 / 分子状酸素 / 酸化反応 / 酸塩基反応 / 酸・塩基反応 / 環境調和 / グリーンケミストリー / 過酸化水素 / ポリオキソメタレート / 固定化触媒 / 金属酸化物

Research Abstract

従来より様々な反応プロセスの不均一系触媒として、担持金属触媒や金属酸化物触媒が用いられてきたが、金属水酸化物に関しては未開拓に近い状態であった。本研究では、溶液中での溶存状態をpH、濃度、温度、溶媒の種類などをコントロールして厳密に制御し、アルミナのような無機酸化物担体上に単核(もしくはそれに近い高分散)のルテニウム水酸化物種を創製することに成功した。このようにして調製した触媒が、光学活性アルコールのラセミ化反応、カルボニル化合物・アリル型アルコールの水素化反応などの水素移行反応対しても非常に有効であることを見出した。種々の物理化学的検討および触媒の構造解析を行ったところ、単核の金属水酸化物種が上記の反応に対する活性点となること、その高活性の要因は「同一金属上に存在する水酸基由来のBronsted 塩基と金属由来のLewis 酸の協働効果」によることを明らかにした。さらに、本研究の触媒設計指針がルテニウム以外の種々の遷移金属種(ロジウム、銅など)にも適用可能で一般性が高いことも示し、これらの水酸基由来のBronsted塩基と金属由来のLewis 酸の協働効果を利用した新しい官能基変換反応(例えば、アミンの酸素化によるアミド合成、アルコールとアンモニアからの直接ニトリル合成)の開発にも成功した。

Research Products

• [Journal Article] Catalytic Oxidative Synthesis of Nitriles Directly from Primary Alcohols and Ammonia (2009)
  • Author(s): Takamichi Oishi, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Angew. Chem. Int. Ed. (in press)
  • Peer Reviewed
• [Journal Article] A Supported Copper Hydroxide as an Efficient, Ligand-free, and Heterogeneous Precatalyst for 1,3-Dipolar Cycloadditions of Organic Azides to Terminal Alkynes (2009)
  • Author(s): Tatsuyori Katayama, Keigo Kamata, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: ChemSusChem 2 Pages: 59-62
  • Peer Reviewed
• [Journal Article] Heterogeneously catalyzed selective N-alkylation of aromatic and heteroaromatic amines with alcohols by a supported ruthenium hydroxide (2009)
  • Author(s): Jung Won Kim, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: J. Catal. 263 Pages: 205-208
  • Peer Reviewed
• [Journal Article] A Tin.Tungsten Mixed Oxide as an Efficient Heterogeneous Catalyst for C.C Bond-Forming Reactions (2009)
  • Author(s): Yoshiyuki Ogasawara, Sayaka Uchida, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Chem. Eur. J. 15 Pages: 4343-4349
  • Peer Reviewed
• [Journal Article] A γ-Keggin-type Dimeric Silicotungstate Sandwiching an Adamantanoid Tetra-nuclear Ruthenium-Oxygen Cluster Core (2008)
  • Author(s): Syuhei Yamaguchi, Kazuhiro Uehara, Keigo Kamata, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Chem. Lett. 37 Pages: 328-329
  • NAID: 10021078683
  • Peer Reviewed
• [Journal Article] Selective aerobic oxidations by supported ruthenium hydroxide catalysts (2008)
  • Author(s): Noritaka Mizuno, Kazuya Yamaguchi
  • Journal Title: Catal. Today 132 Pages: 18-26
  • Peer Reviewed
• [Journal Article] Efficient Oxidative Alkyne Homocoupling Catalyzed by a Monomeric Dicopper-Substituted Silicotungstate (2008)
  • Author(s): Keigo Kamata, Syuhei Yamaguchi, Miyuki Kotani, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 2407-2410
  • Peer Reviewed
• [Journal Article] Synthetic Scope of Ru(OH)_x/Al_2O_3-Catalyzed Hydrogen-Transfer Reactions: An Application to Reduction of Allylic Alcohols via a Sequential Process of Isomerization/Meerwein-Ponndorf-Verley-Type Reduction (2008)
  • Author(s): Jung Won Kim, Takeshi Koike, Miyuki Kotani, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Chem. Eur. J. 14 Pages: 4104-4109
  • Peer Reviewed
• [Journal Article] Synthesis and Catalysis of Di-and Tetranuclear Metal Sandwich-type Silicotungstates [γ-SiW_<10>O_<36>)_2M_2(μ-OH)_2]^K<10-> and [γ-SiW_<10>O_<36>)_2M_4(μ_4-O)(μ-OH)_6]^<8->(M=Zr or Hf) (2008)
  • Author(s): Yuji Kikukawa, Syuhei Yamaguchi, Kazutaka Tsuchida, Yoshinao Nakagawa, Kazuhiro Uehara, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 5472-5478
  • Peer Reviewed
• [Journal Article] Synthesis and structural characterization of a monomeric di-copper-substituted silicotungstate [γ-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): Kazuya Yamaguchi, Keigo Kamata, Syuhei Yamaguchi, Miyuki Kotani, Noritaka Mizuno
  • Journal Title: J. Catal. 258 Pages: 121-130
  • Peer Reviewed
• [Journal Article] A Supported Rhodium Hydroxide Catalyst: Preparation, Characterization, and Scope of the Synthesis of Primary Amides from Aldoximes or Aldehydes (2008)
  • Author(s): Hiroshi Fujiwara, Yoshiyuki Ogasawara, Miyuki Kotani, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Chem. Asian J. 3 Pages: 1715-1721
  • Peer Reviewed
• [Journal Article] Heterogeneously Catalyzed Efficient Oxygenation of Primary Amines to Amides by a Supported Ruthenium Hydroxide Catalyst (2008)
  • Author(s): Jung Won Kim, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 9249-9251
  • Peer Reviewed
• [Journal Article] 1,3-Dipolar Cycloaddition of Organic Azides to Alkynes by a Dicopper-Substituted Silicotungstate (2008)
  • Author(s): Keigo Kamata, Yoshinao Nakagawa, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 15304-15310
  • Peer Reviewed
• [Journal Article] An Efficient One-pot Three-component Reaction to Produce 1,4-Disubstituted-1,2,3-triazoles Catalyzed by a Dicopper-substituted Silicotungstate (2008)
  • Author(s): Kazuya Yamaguchi, Miyuki Kotani, Keigo Kamata, Noritaka Mizuno
  • Journal Title: Chem. Lett. 37 Pages: 1258-1259
  • NAID: 10024398093
  • Peer Reviewed
• [Journal Article] Synthesis of a Dialuminum-Substituted Silicotungstate and Highly Diastereoselective Cyclization of (+)-Citronellal (2008)
  • Author(s): Yuji Kikukawa, Syuhei Yamaguchi, Yoshinao Nakagawa, Kazuhiro Uehara, Sayaka Uchida, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 15872-15878
  • Peer Reviewed
• [Journal Article] Highly Dispersed Ruthenium Hydroxide Supported on Titanium Oxide Effective for Liquid-Phase Hydrogen-Transfer Reactions (2008)
  • Author(s): Kazuya Yamaguchi, Takeshi Koike, Jung Won Kim, Yoshiyuki Ogasawara, Noritaka Mizuno
  • Journal Title: Chem. Eur. J. 14 Pages: 11480-1148
  • Peer Reviewed
• [Journal Article] Heterogeneously Catalyzed Efficient Oxygenation of Primary Amines to Amides by a Supported Ruthenium Hydroxide Catalyst (2008)
  • Author(s): Jung Won Kim, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Angew. Chem. Int. Ed 47 Pages: 9249-9251
  • Peer Reviewed
• [Journal Article] Highly Dispersed Ruthenium Hydroxide Supported on Titanium Oxide Effective for Liquid-Phase Hydrogen-Transfer ReaCtions (2008)
  • Author(s): Kazuya Yamaguchi, Takeshi Koike, Jung Won Kim, Yoshiyuki Ogasawara, Noritaka Mizuno
  • Journal Title: Chem. Eur. J 14 Pages: 11480-11487
  • Peer Reviewed
• [Journal Article] A Supported Rhodium Hydroxide Catalyst : Preparation, Characterization, and Scope of the Synthesis of Primary Amides from Aldoximes or Aldehydes (2008)
  • Author(s): Hiroshi Fujiwara, Yoshiyuki Ogasawara, Miyuki Kotani, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Chem. Asian J 2 Pages: 1715-1721
  • 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] Synthetic Scope of Ru(OH)_x/Al_2O_3-Catalyzed Hydrogen-Transfer Reactions: An Application to Reduction of Allylic Alcohols via a Sequential Process of Isomerization/Meerwein-Ponndorf-Verley-Type Reduction (2008)
  • Author(s): J.W. Kim, T. Koike, M. Kotani, K. Yamaguchi, N. Mizuno
  • Journal Title: Chemistry A European Journal 14 Pages: 4104-4109
  • 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): Keigo Kamata, Miyuki Kotani, Kazuya Yamaguchi, Shiro Hikichi, Noritaka Mizuno
  • Journal Title: Chem. Eur. J. 13 Pages: 639-648
  • Peer Reviewed
• [Journal Article] A Tungsten-Tin Mixed Hydroxide as an Efficient Heterogeneous Catalyst for Dehydration of Aldoximes to Nitriles (2007)
  • Author(s): Kazuya Yamaguchi, Hiroshi Fujiwara, Yoshiyuki Ogasawara, Miyuki Kotani, Noritaka Mizuno
  • Journal Title: Angew. Chem. Int. Ed. 46 Pages: 3922-3925
  • 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): Hiroshi Fujiwara, Yoshiyuki Ogasawara, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Angew. Chem. Int. Ed. 46 Pages: 5202-5205
  • Peer Reviewed
• [Journal Article] Synthesis and Structural Characterization of a γ-Keggin-Type Dimeric Silicotungstate with a Bis(μ-Hydroxo) Dizirconium Core [γ-SiW_<10>O_<36>)_2Zr_2(μ-OH)_2]^<10-> (2007)
  • Author(s): Syuhei Yamaguchi, Yuji Kikukawa, Kazutaka Tsuchida, Yoshinao Nakagawa, Kazuhiro Uehara, Kauzya Yamaguchi, Noritaka Mizuno
  • Journal Title: Inorg. Chem. 46 Pages: 8502-8504
  • 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. Yamaguchi, N. Mizuno
  • Journal Title: Angewandte Chemie International Edition 46 Pages: 5202-5204
  • Peer Reviewed
• [Journal Article] A Tungsten-Tin Mixed Hydroxide as an Efficient Heterogeneous Catalyst for Dehydration of Aldoximes to Nitriles (2007)
  • Author(s): K.Yamaguchi, H.Fujiwara, Y.Ogasawara, M.Kotani, N.Mizuno
  • Journal Title: Angew.Chem.Int.Ed. (in press)
• [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] [γ-1,2-H_2SiV_2W_<10>O_<40>] Immobilized on Surface modified SiO_2 as a Heterogeneous Catalyst for Liquid-phase Oxidation with H_2O_2 (2006)
  • Author(s): Jun Kasai, Yoshinao Nakagawa, Sayaka Uchida, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Chem. Eur. J. 12 Pages: 4176-4184
  • Peer Reviewed
• [Journal Article] Bis(μ-hydroxo) Bridged Di-vanadium-catalyzed Selective Epoxidation of Alkenes with H_2O_2 (2006)
  • Author(s): Noritaka Mizuno, Yoshinao Nakagawa, Kazuya Yamaguchi
  • Journal Title: J. Mol. Catal. A 251 Pages: 286-290
  • Peer Reviewed
• [Journal Article] Ruthenium hydroxide on magnetite as a magnetically separable heterogeneous catalyst for liquid-phase oxidation and reduction (2006)
  • Author(s): Miyuki Kotani, Takeshi Koike, Kazuya Yamaguchi, Noritaka Mizuno
  • Journal Title: Green Chem. 8 Pages: 735-741
  • Peer Reviewed
• [Journal Article] An Immobilized Organocatalyst for Cyanosilylation and Epoxidation (2006)
  • Author(s): Kazuya Yamaguchi, Toru Imago, Yoshiyuki Ogasawara, Jun Kasai, Miyuki Kotani, Noritaka Mizuno
  • Journal Title: Adv. Synth. Catal. 348 Pages: 1516-1520
  • Peer Reviewed
• [Journal Article] Molecular design of selective oxidation catalyst with polyoxometalate (2006)
  • Author(s): Noritaka Mizuno, Shiro Hikichi, Kazuya Yamaguchi, Sayaka Uchida, Yoshinao Nakagawa, Kazuhiro Uehara, Keigo Kamata
  • Journal Title: Catal. Today 117 Pages: 32-36
  • Peer Reviewed
• [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] Bis(μ-hydroxo) Bridged Di-vanadium-catalyzed Selective Epoxidation of Alkenes with H_2O_2 (2006)
  • Author(s): N.Mizuno, Y.Nakagawa, K.Yamaguchi
  • Journal Title: J.Mol.Catal.A 251 Pages: 286-290
• [Journal Article] [γ-1,2-H_2SiV_2W_<10>O_<40>] Immobilized on Surface modified SiO_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] Supported Metal Hydroxides as Effective Heterogeneous Catalysts for Green Functional Transformation (2009)
  • Author(s): Kazuya Yamaguchi
  • Organizer: Asian International Symposium in The 89th Annual Meeting of Chemical Society of Japan
  • Place of Presentation: Funabashi
  • Year and Date: 2009-03-29
• [Presentation] 金属水酸化物を基盤とした高機能固体触媒の開発 (2009)
  • Author(s): 山口 和也
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 船橋
  • Year and Date: 2009-03-27
• [Presentation] 金属水酸化物を基盤とした高機能固体触媒の開発 (2009)
  • Author(s): 山口和也
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日大船橋
  • Year and Date: 2009-03-27
• [Presentation] Supported Metal Hydroxides as Highly Active Heterogeneous Catalysts for Green Functional Group Transformations (2008)
  • Author(s): Kazuya Yamaguchi
  • Organizer: 2nd RSC/CSJ Joint Meeting on Green Chemistry and Sustainability
  • Place of Presentation: Belfast, UK
  • Year and Date: 2008-09-04
• [Presentation] 金属水酸化物の特長を生かした高機能不均一系触媒の開発 (2007)
  • Author(s): 山口和也
  • Organizer: 触媒学会神奈川地区講演会
  • Place of Presentation: 神奈川
  • Year and Date: 2007-10-13
• [Presentation] 金属水酸化物を基盤とした固体触媒による環境調和型酸化反応系の開発 (2007)
  • Author(s): 山口和也
  • Organizer: 第100回触媒討論会「協奏機能触媒」セッション
  • Place of Presentation: 北海道
  • Year and Date: 2007-09-19
• [Presentation] 金属水酸化物を基盤とした固体触媒による環境調和型酸化反応系の開発 (2007)
  • Author(s): 山口和也
  • Organizer: 第100回触媒討論会
  • Place of Presentation: 北海道大学,札幌
  • Year and Date: 2007-09-19
• [Presentation] 触媒による環境に優しいものづくり (2007)
  • Author(s): 山口和也
  • Organizer: 特定領域「極微構造反応」一般公開シンポジウム
  • Place of Presentation: 大阪
  • Year and Date: 2007-05-27
• [Presentation] 金属水酸化物触媒を用いた有機合成 (2007)
  • Author(s): 山口和也
  • Organizer: 触媒学会若手会「夏の研修会」
  • Place of Presentation: 箱根
• [Book] "Activation of Hydrogen Peroxide by Polyoxometalates" Mechanism in Homogeneous and Heterogeneous Catalytic Epoxidation, S. Ted Oyama, eds. (2008)
  • Author(s): Noritaka Mizuno, Kazuya Yamaguchi, Keigo Kamata, Yoshinao Nakagawa
  • Publisher: Elsevier, the Netherlands
• [Book] "固定化水酸化ルテニウム触媒を用いた酸素酸化反応・水和反応"固定化触媒のルネッサンス, 小林修, 小山田秀和 監修 (2007)
  • Author(s): 水野哲孝, 山口和也
  • Publisher: シーエムシー出版
• [Book] 固定化触媒のルネッサンス (2007)
  • Author(s): 水野哲孝, 山口和也
  • Total Pages: 14
  • Publisher: シーエムシー出版
• [Book] "グリーンプロセス"第5版 実験化学講座, 25巻, 触媒化学・電気化学 (2006)
  • Author(s): 水野哲孝, 山口和也
  • Publisher: 丸善株式会社
• [Book] "Liquid Phase Oxidation Catalyzed by Polyoxometalates" Surface and Nanomolecular Catalysis, Ryan M. Richards, eds. (2006)
  • Author(s): Noritaka Mizuno, Keigo Kamata, Kazuya Yamaguchi
  • Publisher: Taylor and Francis Group, LLC., New York
• [Book] Surface and Nanomolecular Catalysis(分担執筆)"Liquid Phase Oxidation Catalyzed by Polyoxometalates" (2006)
  • Author(s): N.Mizuno, K.Kamata, K.Yamaguchi
  • Total Pages: 30
  • Publisher: Taylor and Francis Group, LLC.