Development of Aquacatalytic Polymer-Dispersed Nanometal Composites

• Project/Area Number: 15205015
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Institute for Molecular Science (2004-2006); Okazaki National Research Institutes (2003)
• Principal Investigator: UOZUMI Yasuhiro Institute for Molecular Science, Research Center for Molecular-scale Nanoscience, Professor, 分子スケールナノサイエンスセンター, 教授 (90201954)
• Project Period (FY): 2003 – 2006
• Project Status: Completed (Fiscal Year 2006)
• Budget Amount: ¥50,830,000 (Direct Cost: ¥39,100,000、Indirect Cost: ¥11,730,000); Fiscal Year 2006: ¥11,050,000 (Direct Cost: ¥8,500,000、Indirect Cost: ¥2,550,000); Fiscal Year 2005: ¥11,050,000 (Direct Cost: ¥8,500,000、Indirect Cost: ¥2,550,000); Fiscal Year 2004: ¥11,050,000 (Direct Cost: ¥8,500,000、Indirect Cost: ¥2,550,000); Fiscal Year 2003: ¥17,680,000 (Direct Cost: ¥13,600,000、Indirect Cost: ¥4,080,000)
• Keywords: Nanometal / palladium, platinum / catalysis in water / immobilization / pincer complex / amphiphilic polymer

Research Abstract

An amphiphilic resin-dispersion of nanoparticles of platinum and palladium were developed which exhibited high catalytic activity in aerobic oxidation of a wide variety of alcohols in water with an oxygen or air atmosphere. A novel solid-phase 3D metal-organic coordination network catalyst was prepared via self-assembly from PdC12(CH3CN)2 and a trisphosphine hub with three flexible alkylchain linkers.
A novel solid-phase self-organized catalyst of palladium nanoparticles was prepared from PdC12 with main-chain viologen polymers via complexation and reduction. This insoluble nanocatalyst nano-Pd catalyst efficiently promoted a-alkylation of ketones with primary alcohols. A tightly convoluted polymeric phosphotungstate catalyst was prepared via ionic-assembly of H3PW12040 and poly (alkylpyridinium).
An oxidative cyclization of various alkenols and alkenoic acids was efficiently promoted by the polymeric catalyst. The pincer complexes bearing a plane coordination structure and functional substituents were prepared to realize stereoselective catalysis and supra complex formation.

Research Products

• [Journal Article] Asymmetric π -allylic etherification of cycloalkenyl esters with phenols in water using a resin-supported chiral palladium complex (2006)
  • Author(s): Yasuhiro Uozumi, Masahiro Kimura
  • Journal Title: Tetrahedron : Asymmetry 17 Pages: 161-166
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] A Solid-Phase Self-Organized Catalyst of Nanopalladium with Main-Chain Viologen Polymers : alfa-Alkylation of Ketones with Primary Alcohols (2006)
  • Author(s): Yoichi M.A.Yamada, Yasuhiro Uozumi
  • Journal Title: Organic Letters 8 Pages: 1375-1378
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Amphezonol A, a novel polyhydroxyl metabolite from marine dinoflagellate Amphidinium sp. (2006)
  • Author(s): Takaaki Kubota, Yusuke Sakuma, Kazutaka Shimbo, Masashi Tsuda, Michiko Nakano, Yasuhiro Uozumi, Junichi Kobayashi
  • Journal Title: Tetrahedron Letters 47 Pages: 4369-4371
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Novel 3D Coordination Palladium-Network Complex : A Recyclable Catalyst for Suzuki-Miyaura Reaction (2006)
  • Author(s): Yoichi M.A.Yamada, Yasunari Maeda, Yasuhiro Uozumi
  • Journal Title: Organic Letters 8 Pages: 4259-4262
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] π-Allylic Azidation in Water with an Amphiphilic Resin-Supported Palladium-Phosphine Complex (2006)
  • Author(s): Yasuhiro Uozumi, Toshimasa Suzuka, Ray Kawade, Hiroe Takenaka
  • Journal Title: Synlett Pages: 2109-2113
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] PCP Pincer Palladium Complexes and Their Catalytic Properties : Synthesis via the Electrophilic Ligand Introduction Route (2006)
  • Author(s): Tsutomu Kimura, Yasuhiro Uozumi
  • Journal Title: Organometallics 25 Pages: 4883-4887
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] A Combinatorial Approach to Heterogeneous Asymmetric Aquacatalysis with Amphiphilic Polymer-Supported Chiral Phosphine-Palladium Complexes (2006)
  • Author(s): Yukinari Kobayashi, Daiki Tanaka, Hiroshi Danjo, Yasuhiro Uozumi
  • Journal Title: Advanced Synthesis ＆ Catalysis 348 Pages: 1561-1566
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] π -Allylic C1-Substitution in Water with Nitromethane Using Amphiphilic Resin-Supported Palladium Complexes (2006)
  • Author(s): Yasuhiro Uozumi, Toshimasa Suzuka
  • Journal Title: The Journal of Organic Chemistry 71 Pages: 8644-8646
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Alkylative Cyclization of 1,6-Enynes in Water with an Amphiphilic Resin-Supported Palladium Catalyst (2006)
  • Author(s): Yasushi Nakai, Tsutomu Kimura, Yasuhiro Uozumi
  • Journal Title: Synlett Pages: 3065-3068
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Instantaneous Carbon-Carbon Bond Formation Using a Microchannel Reactor with a Catalytic Membrane (2006)
  • Author(s): Yasuhiro Uozumi, Yoichi M.A.Yamada, Tomohiko Beppu, Naoshi Fukuyama, Masaharu Ueno, Takehiko Kitamori
  • Journal Title: Journal of The American Chemical Society 128 Pages: 15994-15995
  • Description: 「研究成果報告書概要(和文)」より
• [Journal Article] Asymmetric π-allylic etherification of cycloalkenyl esters with phenols in water using a resin-supported chiral palladium complex (2006)
  • Author(s): Yasuhiro Uozumi, Masahiro Kimura
  • Journal Title: Tetrahedron : Asymmetry 17 Pages: 161-166
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Amphezonol A, a novel polyhydroxyl metabolitee from marine dinoflagellate Amphidiniium sp (2006)
  • Author(s): Takaaki Kubota, Yusuke Sakuma, Kazutaka Shimbo, Masashi Tsuda, Michiko Nakano, Yasuhiro Uozumi, Junichhi Kobayashi
  • Journal Title: Tetrahedron Letters 47
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] A Combinatorial Approach to Heterogeneous Asymmetric Aquacatalysis with Amphiphilic Polymer- Supported Chiral Phosphine-Palladium Complexes (2006)
  • Author(s): Yukinari Kobayashi, Daiki Tanaka, Hiroshi Danjo, Yasuhiro Uozumi
  • Journal Title: Advanced Synthesis ＆ Catalysis 348 Pages: 1561-1566
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] π-Allylic Cl-Substitution in Water with Nitromethane Using Amphiphilic Resin-Supported Palladium Complexe (2006)
  • Author(s): Yasuhiro Uozumi, Toshimasa Suzuka
  • Journal Title: The Journal of Organic Chemistry 71 Pages: 8644-8646
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] Alkylative Cyclization of 1,6-Enynes in Water with an Amphiphilic Resin-Supported Palladium Catalyst (2006)
  • Author(s): Yasushi Nakai, Tsutomu Kimura, Yasuhiro Uozumi.
  • Journal Title: Synlett Pages: 305-3068
  • Description: 「研究成果報告書概要(欧文)」より
• [Journal Article] A Solid-phase Self-Organized Catalyst of Nanopalladium with Main-Chain Viologen Polymers : alfa-Alkylation of Ketones with Primary Alcohols (2006)
  • Author(s): Yoichi M, A.Yamada, Yasuhiro Uozumi
  • Journal Title: Organic Letters 8 Pages: 1375-1378
• [Journal Article] Novel 3D Coordination Palladium-Network Complex : A Recyclable Catalyst for Suzuki-Miyaura Reaction (2006)
  • Author(s): Yoichi M, A.Yamada, Yasunari Maeda, Yasuhiro Uozumi
  • Journal Title: Organic Letters 8 Pages: 4259-4262
• [Journal Article] A Combinatorial Approach to Heterogeneous Asymmetric Aqua catalysis with Amphiphilic Polymer-Supported Chiral Phosphine-Palladium Complexes (2006)
  • Author(s): Yukinari Kobayashi, Daiki Tanaka, Hiroshi Danjo, Yasuhiro Uozumi
  • Journal Title: Advanced Synthesis ＆ Catalysis 348 Pages: 1561-1566
• [Journal Article] π-Allylic C1-Substitution in Water with Nitro methane Using Amphiphilic Resin-Supported Palladium Complexes (2006)
  • Author(s): Yasuhiro Uozumi, Toshimasa Suzuka
  • Journal Title: The Journal of Organic Chemistry 71 Pages: 8644-8646
• [Journal Article] Instantaneous Carbon-Carbon Bond Formation Using a Micro channel Reactor with a Catalytic Membrane (2006)
  • Author(s): Yasuhiro Uozumi, Yoichi M, A.Yamada, Tomohiko Beppu, Naoshi Fukuyama, Masaharu Ueno, Takehiko Kitamori
  • Journal Title: Journal of The American Chemical Society 128 Pages: 15994-15995
• [Journal Article] Hydrogenation and Dehalogenation under Aqueous Conditions with an Amphiphilic-Polymer-Supported Nanopalladium Catalyst (2005)
  • Author(s): Ryu Nakao, Hakjyune Rhee, Yasuhiro Uozumi*
  • Journal Title: Organic Letters 7 Pages: 163-165
• [Journal Article] Cycloisomerization of 1,6-Enynes : Asymmetric Multistep Preparation of a Hydrindane Framework in Water with Polymeric Catalysts (2005)
  • Author(s): Yasushi Nakai, Yasuhiro Uozumi*
  • Journal Title: Organic Letters 7 Pages: 291-293
• [Journal Article] Controlled Monoarylation of Dibromoarenes in Water with a Polymeric Palladium Catalyst (2005)
  • Author(s): Yasuhiro Uozumi, Makoto Kikuchi
  • Journal Title: Synlett Pages: 1775-1778
• [Journal Article] NCN Pincer Palladium Complexes ; Their Preparation via Ligand Introduction Route and Their Catalytic Properties (2005)
  • Author(s): Kazuhiro Takenaka, Maki Minakawa, Yasuhiro Uozumi
  • Journal Title: Journal of the American Chemical Society 127 Pages: 12273-12281
• [Journal Article] 高分子固定化遷移金属触媒による水中有機変換反応 (2005)
  • Author(s): 魚住 泰広
  • Journal Title: 触媒学会 47(NO.7) Pages: 550-555
• [Journal Article] PS-PEG resin-supported palladium-MOP complexes, Application in asymmetric π-allylic reduction (2004)
  • Author(s): Heiko Hocke, Yasuhiro Uozumi
  • Journal Title: Tetrahedron 60 Pages: 9297-9306
• [Journal Article] Development of Chiral Pincer Palladium Complexes Bearing a Pyrroloimidazolone Unit. Catalytic Use for Asymmetric Michael Addition (2004)
  • Author(s): Kazuhiro Takenaka, Yasuhiro Uozumi
  • Journal Title: Organic Lett. 6(No11) Pages: 1833-1835
• [Journal Article] Deuterium-Labeling Studies Establishing Stereochemistry at the Oxypalladation Step in Wacker-Type Oxidative Cyclization of an o-Allylphenol (2004)
  • Author(s): Tamio Hayashi, Kaori Yamasaki, Michihiro Mimura, Yasuhiro Uozumi
  • Journal Title: J.Am.Chem.Soc. 126 Pages: 3036-3037
• [Journal Article] Asymmetric Allylic Amination in Water Catalyzed by an Amphiphilic Resin-Supported Chiral Palladium Complex (2004)
  • Author(s): Yasuhiro Uozumi, Hirotaka Tanaka, Kazutaka Shibatomi
  • Journal Title: Organic Lett. 6 Pages: 281-283
• [Book] Recent Progress in Polymeric Palladium Catalysts for Organic Synthesis (2004)
  • Author(s): Yasuhiro Uozumi
  • Publisher: Topics in Current Chemistry
• [Publications] Uozumi, Yasuhiro, Tanaka, Hirotaka, Shibatomi, Kazutaka: "Asymmetric Allylic Amination in Water Catalyzed by an Amphiphilic Resin-Supported Chiral Palladium Complex"Org.Lett.. 6. 281-283 (2004)
• [Publications] Hocke, Heiko, Uozumi, Yasuhiro: "A Simple Synthetic Approach to Homochiral 6- and 6'-substituted 1,1'-Binaphthyl Derivatives"Tetrahedron. 59. 619-630 (2003)
• [Publications] 魚住 泰広: "水中機能性固定化パラジウム錯体触媒反応"ファルマシア. 39. 647-649 (2003)
• [Publications] 魚住 泰広: "先端科学シリーズI 有機金属/キラル/触媒/高分子 日本化学会編 不斉工程開発へのコンビナトリアルアプローチ"丸善株式会社. 99-105 (2003)
• [Publications] 魚住 泰広: "先端科学シリーズV 海洋天然物/錯体/コンビナトリアル/全合成 日本化学会編 錯体触媒反応における近年のブレークスルー"丸善株式会社. 93-98 (2003)