均一・不均一系触媒化学の概念融合による協奏機能触媒の創成

2009 Fiscal Year Annual Research Report

• Project/Area Number: 18065010
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: 碇屋 隆雄 Tokyo Institute of Technology, 大学院・理工学研究科, 教授 (30107552)
• Co-Investigator(Kenkyū-buntansha): 水野 哲孝 東京大学, 大学院・工学系研究科, 教授 (50181904) ; 金田 清臣 大阪大学, 太陽エネルギー化学研究センター, 教授 (90029554) ; 小江 誠司 九州大学, 未来化学創造センター, 教授 (60290904) ; 小宮 三四郎 東京農工大学, 大学院・共生科学技術研究院, 教授 (00111667)
• Keywords: 均一系触媒 / 不均一系触媒 / 触媒・化学プロセス / 有機工業化学 / 合成化学

Research Abstract

本領域研究では、均一系および不均一系触媒化学の協奏的融合による新たな協奏機能触媒化学を確立することを目指してきた。そのため、金属錯体を基本とする分子性触媒の研究者と、分子・原子レベルで固体表面修飾や機能との相関、固体担体と触媒活性中心の解明を行っている固体触媒研究者に加えて、金属集積と協同機能を開拓する多金属触媒の研究者および生体触媒機能を模倣して、実用触媒の開発をめざす生体模倣の触媒研究者を中心に研究推進してきた。
最終年度は、前年度に引き続き、19名の計画班員と63名の公募班員が、A01「分子機能触媒化学」A02「多金属機能触媒化学」、A03「固体機能触媒化学」、A04「生体模倣機能触媒化学」、の研究項目を分担し、相互連携をとりつつ研究推進した。結果として、第6回公開シンポジウムを4月に,第7回を平成22年3月に2回開催して本領域研究における最先端の研究成果を広く公開できた。特に7回の最終報告会では、各班のリーダーが、4年間の研究成果を総括するとともに、協奏機能触媒への取り組みの成果をまとめて報告し、高い評価を受けた。さらに、昨年に引き続き協奏機能触媒の概念をより広く広めるため、日本化学会、触媒学会や錯体化学討論会に協力し、合同シンポジウムを開催して,広く他分野の研究者との討論を積極的に実施した結果、協奏機能触媒の概念が広く深く浸透したものと考えている。また、国際会議を北海道大学においてノーベル化学賞受賞のGrubbs先生他3名を招聘し、協奏機能触媒の概念が世界的に認められ、高い評価を受けた。さらに、特定領域研究グループ間での共同論文や学会発表など、多くの成果をあげることができた。
総じて、4年間、評価班の先生のご支援ご助言のもとに、領域研究を円滑に運営でき、期待以上の成果をあげることができた。

Research Products

• [Journal Article] In Situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy of MCM-41 Mesoporous Silica : Mechanistic Consideration on the Chemical Fixation of CO_2 with N,N'-Dimethylethylenediamine to 1,3-Dimethyl-2-imidazolidinone (2009)
  • Author(s): Seki, T., Ikariya, T.
  • Journal Title: Chem.Commun. 11 Pages: 10073-10079
  • Peer Reviewed
• [Journal Article] Palladium-catalyzed Carboxylative Cyclization of α-Allenyl Amines in Dense Carbon Dioxide (2009)
  • Author(s): Kayaki, Y., Mori, N., Ikariya, T.
  • Journal Title: Tetrahedron Lett. 50 Pages: 6491-6493
  • Peer Reviewed
• [Journal Article] N-Heterocyclic Carbenes as Efficient Organocatalysts for CO_2 Fixation Reactions (2009)
  • Author(s): Kayaki, Y., Yamamoto, M., Ikariya, T.
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 4194-4197
  • Peer Reviewed
• [Journal Article] (η^6-arene)Ru^<II>/Chiral SN Ligand : A Novel Bifunctional Catalyst System for Asymmetric Transfer Hydrogenation of Aromatic Ketones (2009)
  • Author(s): Ito, M., Shibata, Y., Watanabe, A., Ikariya, T.
  • Journal Title: Synlett 10 Pages: 1621-1626
  • Peer Reviewed
• [Journal Article] Synthesis of Parent Amido(NH_2)-Bridged Dinuclear Complexes of Ruthenium and Iridium by Stepwise transfer Hydrogenation of μ-Azido Complexes (2009)
  • Author(s): Kimura, T., Arita, H., Ishiwata, K., Kuwata, S., Ikariya, T.
  • Journal Title: Dalton Trans. Pages: 2912-2914
  • Peer Reviewed
• [Journal Article] Hydrogen- and Oxygen-Driven Interconversion between Imido-Bridged Dirhodium(III)and Amido-Bridged Dirhodium(II)Complexes (2009)
  • Author(s): Ishikawa, K., Kuwata, S., Ikariya, T.
  • Journal Title: J.Am.Chem.Soc. 131 Pages: 5001-5009
  • Peer Reviewed
• [Journal Article] Bifunctional Transition Metal-Based Molecular Catalysts for Asymmetric C-C and C-N Bonds Formation (2009)
  • Author(s): Gridnev, I.D., Ikariya, T.
  • Journal Title: Chem.Rec. 9 Pages: 106-123
  • Peer Reviewed
• [Journal Article] Hydrogenation of N-Acylcarbamates and Sulfonamides Catalyzed by Bifunctional Cp^*Ru(PN)Complex (2009)
  • Author(s): Ito, M., Koo, L.W., Himizu, A., Kobayashi, C., Sakaguchi, A., Ikariya, T.
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 1324-1327
  • Peer Reviewed
• [Journal Article] Remarkable Positive Effect of Silver Salts on Asymmetric Hydrogenation of Acyclic Imines with Cp*Ir Complexes Bearing Chiral N-Sulfonylated Diamine Ligands (2009)
  • Author(s): Shirai, S., Nara, H., Kayaki, Y., Ikariya, T.
  • Journal Title: Organometallics 28 Pages: 802-809
  • Peer Reviewed
• [Journal Article] A Convenient Method for the Synthesis of Protic 2-tert-Phosphino-1-Amines and Their Cp*RuCI Complexes (2009)
  • Author(s): Ito, M., Osaku, A., Kobayashi, C., Shiibashi, A., Ikariya, T.
  • Journal Title: Organometallics 28 Pages: 390-393
  • Peer Reviewed
• [Journal Article] Mesoporous Silica-Catalysed Continuous Chemical Fixation of CO_2 with N,N'-dimethylethylenediamine in Supercritical CO_2 :_Efficient Synthesis of 1,3-Dimethyl-2-imidazolidinone (2009)
  • Author(s): Seki, T., Kokubo, Y., Ichikawa, S., Suzuki, T., Kayaki, Y., Ikariya, T.
  • Journal Title: Chem.Commun. Pages: 349-351
  • Peer Reviewed
• [Journal Article] Synthesis and Structure of Novel(η^1:η^6-aminoalkylarene)Ru^<II> Complexes (2009)
  • Author(s): Ito, M., Komatsu, H., Endo, Y., Ikariya, T.
  • Journal Title: Chem.Lett. 38 Pages: 98-99
  • Peer Reviewed
• [Journal Article] Reaction of an Oxaruthenacycle with DMAD. Stoichiometric Transformations of 2,6-Xylenol to Allylic Phenols and Benzopyrans via sp^3 C-H Bond Cleavage Reaction (2009)
  • Author(s): Hirano, M., Izhab, I.B., Kurata, N., Komine, N., Komiya, S.
  • Journal Title: Dalton Trans. Pages: 3270-3279
  • Peer Reviewed
• [Journal Article] Visible Light Enhanced Selective Reductive Elimination of Methylmanganese Complex from Heterodinuclear Dimethylphenyl(4,4'-di-tert-butyl-2,2-bipyridine)platinum-pentacarbonylmanganese Complex (2009)
  • Author(s): Komiya, S., Ezumi, S., Komine, N., Hirano, M.
  • Journal Title: Organometallics 28 Pages: 3608-3610
  • Peer Reviewed
• [Journal Article] Isolation of trans-2, 5-Bis(methoxycarbonyl)ruthenacyclopentane by Oxidative Coupling of Methyl Acrylate on Ruthenium(O)as an Active Intermediate for Tail-to-tail Selective Catalytic Dimerization (2009)
  • Author(s): Hirano, M., Sakate, Y., Komine, N., Komiya, S., Bennet, M.A.
  • Journal Title: Organometallics 28 Pages: 4902-4905
  • Peer Reviewed
• [Journal Article] Synthesis of Heterodinuclear(Carbene)platinum(or Palladium)Complex That Gives μ-Alkenyl-Type Complex by Deprotonation (2009)
  • Author(s): Tanaka, S., Komine, N., Hirano, M., Komiya, S.
  • Journal Title: Organometallics 28 Pages: 5368-5381
  • Peer Reviewed
• [Journal Article] Hydrogen-Bond-Assisted Epoxidation of Homoallylic and Allylic with Hydrogen Peroxide Catalyzed by Selenium-Containing Dinuclear Peroxotungstate (2009)
  • Author(s): Kamata, K., Hirano, T., Kuzuya, S., Mizuno, N.
  • Journal Title: J.Am.Chem.Soc. 131 Pages: 6997-7004
  • Peer Reviewed
• [Journal Article] Highly Efficient Oxidation of Sulfide with Hydrogen Peroxide Catalyzed by[SeO_4{WO(O_2)_2)_2]^<2-> (2009)
  • Author(s): Kamata, K., Hirano, T., Mizuno, N.
  • Journal Title: Chem.Commun. Pages: 3958-3960
  • Peer Reviewed
• [Journal Article] Highly Selective Oxidation of Organosilanes to Silanols with Hydrogen Peroxide Catalyzed by Lacunary Polyxotungstate (2009)
  • Author(s): Ishimoto, R., Kamata, K., Mizuno, N.
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 8900-8904
  • Peer Reviewed
• [Journal Article] Efficient Catalytic Synthesis of Tertiary and Secondary Amines from Alcohols and Urea (2009)
  • Author(s): He, J.L., Kim, J.W., Yamaguchi, K., Mizuno, N.
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 9888-9891
  • Peer Reviewed
• [Journal Article] Aerobic Alcohol Oxidation Catalyzed by Supported Ruthenium Hydroxides (2009)
  • Author(s): Yamaguchi, K., Kim, J.W., He, J.L., Mizuno, N.
  • Journal Title: J.Catal. 268 Pages: 343-349
  • Peer Reviewed
• [Journal Article] Micelles and Vesicles Formed by Polyoxometalate-Block Copolymer Composites (2009)
  • Author(s): Bu, W., Uchida, S., Mizuno, N.
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 8281-8284
  • Peer Reviewed
• [Journal Article] A Supported Copper Hydroxide on Titanium Oxide as Efficient Reusable Heterogeneous Catalyst for 1,3-Dipolar Cycloaddition of Organic Azides to Terminal Alkynes (2009)
  • Author(s): Yamaguchi, K., Oishi, T., Katayama, T., Mizuno, N.
  • Journal Title: Chem.-Eur.J. 15 Pages: 10464-10472
  • Peer Reviewed
• [Journal Article] Heterogeneously Catalyzed One-pot Synthesis of Aldimines from Primary Alcohols and Amines by Supported Ruthenium Hydroxides (2009)
  • Author(s): Kim, J.W., He, J.L., Yamaguchi, K., Mizuno, N.
  • Journal Title: Chem.Lett. 38 Pages: 920-921
  • Peer Reviewed
• [Journal Article] Inorganic Cryptand : Size-selective Strong Metallic Cation Encapsulation by Disilicoicosatungstate(Si_2W_<20>)Polyoxometalate (2009)
  • Author(s): Yoshida, A., Nakagawa, Y., Uehara, K., Hikichi, S., Mizuno, N.
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 7055-7058
  • Peer Reviewed
• [Journal Article] Catalytic Oxidative Synthesis of Nitriles Directly from Primary Alcohols and Ammonia (2009)
  • Author(s): Oishi, T., Yamaguchi, K., Mizuno, N.
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 6286-6288
  • Peer Reviewed
• [Journal Article] Heterogeneously Catalyzed Efficient Alkyne-Alkyne Homocoupling by a Supported Copper Hydroxide on Titanium Oxide (2009)
  • Author(s): Oishi, T., Katayama, T., Yamaguchi, K., Mizuno, N.
  • Journal Title: Chem.-Eur.J. 15 Pages: 7539-7542
  • Peer Reviewed
• [Journal Article] Size-Selective Sorption of Small Organic Molecules in One-Dimensional Channel of Organic-Inorganic Hybrid Ionic Crystal Stabilized by π-π Interaction (2009)
  • Author(s): Tagami, H., Uchida, S., Mizuno, N.
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 6160-6165
  • Peer Reviewed
• [Journal Article] An Efficient Solvent-Free Route to Silyl Esters and Silyl Ethers (2009)
  • Author(s): Ojima, Y., Yamaguchi, K., Mizuno, N.
  • Journal Title: Adv.Synth.Catal. 351 Pages: 1405-1411
  • Peer Reviewed
• [Journal Article] Design, Synthesis, and Catalysts of Bio-inspired Immobilized Metallocomplex Catalyst (2009)
  • Author(s): Hikichi, S., Kaneko, M., Miyoshi, Y., Mizuno, N., Fujita, K., Akita, M.
  • Journal Title: Top.Catal. 52 Pages: 845-851
  • Peer Reviewed
• [Journal Article] A Tin-Tungsten Mixed Oxide as an Efficient Heterogeneous Catalyst for C-C Bond-Forming Reactions (2009)
  • Author(s): Ogasawara, Y., Uchida, S., Yamaguchi, K., Mizuno, N.
  • Journal Title: Chem.-Eur.J. 15 Pages: 4343-4349
  • Peer Reviewed
• [Journal Article] Supported Gold Nanoparticles as a Reusable Catalyst for Synthesis of Lactones from Diols Using Molecular Oxygen as an Oxidant under Mild Conditions (2009)
  • Author(s): Mitsudome, T., Noujima, A., Mizugaki, T., Jitsukawa, K., Kaneda, K.
  • Journal Title: Green Chem. 11 Pages: 793-797
  • Peer Reviewed
• [Journal Article] Supported Silver Nanoparticle Catalyst for Selective Hydration of Nitriles to Amides in Water (2009)
  • Author(s): Mitsudome, T., Mikami, Y., Mori, H., Arita, S., Mizugaki, T.Jitsukawa, K., Kaneda, K.
  • Journal Title: Chem.Commun. Pages: 3258-3260
  • Peer Reviewed
• [Journal Article] Supported Gold Nanoparticle Catalyst for the Selective Oxidation of Silanes to Silanols in Water (2009)
  • Author(s): Mitsudome, T., Noujima, A., Mizugaki, T., Jitsukawa, K., Kaneda, K.
  • Journal Title: Chem.Commun. Pages: 5302-5304
  • Peer Reviewed
• [Journal Article] Efficient Aerobic Oxidation of Alcohols using a Hydrotalcite-Supported Gold Nanoparticle Catalyst (2009)
  • Author(s): Mitsudome, T., Noujima, A., Mizugaki, T., Jitsukawa, K., Kaneda, K.
  • Journal Title: Adv.Synth.Catal. 351 Pages: 1890-1896
  • Peer Reviewed
• [Journal Article] Development of Concerto Metal Catalysts Using Apatite Compounds for Green Organic Syntheses (2009)
  • Author(s): Kaneda, K., Mizugaki, T.
  • Journal Title: Energy Environ.Sci. 2 Pages: 655-673
  • Peer Reviewed
• [Journal Article] Oxidant-Free Lactonization of Diols Using Hydrtalcite-Supported Copper Catalsyts (2009)
  • Author(s): Mikami, Y., Ebata, K., Mitsudome, T., Mizugaki, T., Jitsukawa, K., Kaneda, K.
  • Journal Title: Heterocycles 80 Pages: 855-861
  • Peer Reviewed
• [Journal Article] Creation of a Monomeric Vanadate Species in an Apatite Framework as an Active Heterogeneous Base Catalyst for Michael Reactions in Water (2009)
  • Author(s): Kaneda, K., Hara, T., Hashimoto, N., Mitsudome, T., Mizugaki, T., Jitsukawa, K.
  • Journal Title: Catal.Today 10 Pages: 1016-1016
  • Peer Reviewed
• [Journal Article] Controlled Synthesis of Pd Clusters in Subnanometer Range Using Poly(propylene imine)Dendrimers (2009)
  • Author(s): Mizugaki, T., Kibata, T., Ota, K., Mitsudome, T., Ebitani, K., Jitusukawa, K., Kaneda, K.
  • Journal Title: Chem.Lett. 38 Pages: 1118-1119
  • Peer Reviewed
• [Journal Article] Electorons from Hydrogen (2009)
  • Author(s): Ogo, S.
  • Journal Title: Chem.Commun. Pages: 3317-3325
  • Peer Reviewed
• [Journal Article] Critical Aspects of[NiFe]hydrogenase Ligand Composition (2009)
  • Author(s): Ogo, S., Matsumoto, T., Ichikawa, K.
  • Journal Title: Dalton Trans. Pages: 4304-4309
  • Peer Reviewed
• [Presentation] ポリオキソメタレートを用いた精密触媒設計 (2010)
  • Author(s): 水野哲孝
  • Organizer: 触媒学会 愛媛地区講演会―高度に制御された活性点を利用した触媒化学―
  • Place of Presentation: 松山
  • Year and Date: 2010-01-22
• [Presentation] Water/Hexane Biphasic Interface Contorolled Regioselective Palladium-Catalyzed Allylation of Benzenethiol (2009)
  • Author(s): Sanshiro Komiya
  • Organizer: International Symposium on Catalysis and Fine Chemicals 2009
  • Place of Presentation: Seoul, Korea
  • Year and Date: 2009-12-16
• [Presentation] Visible Light Enhanced Reductive Elimination of Methylmanganese from Heterodinuclear Triorganoplatinum-managanese Complex (2009)
  • Author(s): Sanshiro Komiya
  • Organizer: 14th Japan-Korea Joint Symposium on Organometallic and Coordination Chemistry
  • Place of Presentation: 名古屋
  • Year and Date: 2009-10-10
• [Presentation] Recent Progress in Concerto Molecular Catalysis, Aerobic Oxidation of Alcohols with Bifunctional Molecular Catalysis (2009)
  • Author(s): 碇屋隆雄
  • Organizer: 14th Japan-Korea Joint Symposium on Organometallic and Coordination Chemistry
  • Place of Presentation: 名古屋
  • Year and Date: 2009-10-08
• [Presentation] Green Oxidation Reactions by Polyoxometalate-Based Catalysts (2009)
  • Author(s): 水野哲孝
  • Organizer: International Symposium on Relations between Homogeneous and Heterogeneous Catalysis XIV
  • Place of Presentation: Stockholm, Sweden
  • Year and Date: 2009-09-17
• [Presentation] Recent Progress in Concerto Molecular catalysis (2009)
  • Author(s): 碇屋隆雄
  • Organizer: International Symposium On Homogeous and Heteogeneous Catalysis XIV
  • Place of Presentation: Stockholm, Sweden
  • Year and Date: 2009-09-13
• [Presentation] 分子の収着・分離、変換場となるポリオキソメタレート複合体の創製 (2009)
  • Author(s): 水野哲孝
  • Organizer: 第3回日本化学会関東支部大会
  • Place of Presentation: 東京
  • Year and Date: 2009-09-05
• [Presentation] Concerto Molecular Catalysts for Reductive and Oxidative Transformation (2009)
  • Author(s): 碇屋隆雄
  • Organizer: 15th IUPAC Symposium(OMCOS 15)
  • Place of Presentation: Glasgow, Scotland
  • Year and Date: 2009-07-26
• [Presentation] An Efficient Oxidative Alkyne-Alkyne Homocoupling by a Dicopper-Substituted Silicotungstate (2009)
  • Author(s): 水野哲孝
  • Organizer: 6th World Congress on Oxidation Catalysis
  • Place of Presentation: Lille, France
  • Year and Date: 2009-07-07
• [Presentation] 協奏機能分子触媒の化学 (2009)
  • Author(s): 碇屋隆雄
  • Organizer: 第42回有機金属若手の会
  • Place of Presentation: 岐阜
  • Year and Date: 2009-07-06
• [Remarks]
  • URL: http://concerto.cstm.kyushu-u.ac.jp/
• [Patent(Industrial Property Rights)] アミド類およびラクタム類の実用的な還元方法 (2009)
  • Inventor(s): 碇屋隆雄, 伊藤正人, 大塚隆史
  • Industrial Property Rights Holder: 碇屋隆雄, 伊藤正人, 大塚隆史
  • Industrial Property Number: 特願2009-285820
  • Filing Date: 2009-12-17