高活性高分子触媒の創製と連続フローシステム化

• Project Area: Middle molecular strategy: Creation of higher bio-functional molecules by integrated synthesis.
• Project/Area Number: 18H04431
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Research Institution: Institute for Molecular Science
• Principal Investigator: 魚住 泰広 分子科学研究所, 生命・錯体分子科学研究領域, 教授 (90201954)
• Project Period (FY): 2018-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2019: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000); Fiscal Year 2018: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
• Keywords: 有機化学 / 化学プロセス / 有機工業化学 / 触媒・化学プロセス

Outline of Annual Research Achievements

本課題では両親媒性高分子担体にパラジウム，銅，白金などの遷移金属錯体あるいはナノ粒子を担持することで水中・不均一条件下での精密有機分子変換を円滑に実施しうる反応駆動システムを確立し，さらにそれら固体担持触媒をカートリッジに充填することで連続フロー反応に適用した。特に高分子担持銅錯体触媒を用いたHuisgen反応を確立し，世界的に利用されている医薬品タゾバクタムの連続フロー合成へと展開した。また白金ナノ粒子触媒による連続フロー水素化反応では化学選択的なアルデヒドの水素化還元反応を実現した。
また遷移金属触媒反応の開発過程で末端アルキン類のアリール化反応をppm触媒量のパラジウムで達成可能な反応系を確立した。固定化触媒の創製検討過程では高分子固定化スルホン酸触媒を開発し，さらに同固定化触媒をカートリッジ化したことで，カルボン酸とアルコールからの脱水的直接エステル化反応（平衡反応）の連続フロー化を行い平衡定数を超えた高効率エステル化を実現している。
両親媒性高分子担持パラジウム錯体触媒は３班計画班員：大嶋孝志（九州大学）との共同研究に適用された。また３班公募班員：林雄二郎（東北大学）との共同研究を実施し，林らが開発した光学活性有機触媒を高分子担持することで有機触媒不斉合成反応の連続フローによる実施に道を拓いた。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] 三峡大学(中国)
• [Int'l Joint Research] カレス大学(チェコ)
• [Journal Article] Production of Bio Hydrofined Diesel, Jet Fuel, and Carbon Monoxide from Fatty Acids Using a Silicon Nanowire Array-Supported Rhodium Nanoparticle Catalyst under Microwave Conditions (2020)
  • Author(s): Baek Heeyoel、Kashimura Keiichiro、Fujii Takashi、Tsubaki Shuntaro、Wada Yuji、Fujikawa Shigenori、Sato Takuma、Uozumi Yasuhiro、Yamada Yoichi M. A.
  • Journal Title: ACS Catalysis Volume: 10 Issue: 3 Pages: 2148-2156
  • DOI: 10.1021/acscatal.9b04784
  • Peer Reviewed
• [Journal Article] Mechanistic insight into the catalytic hydrogenation of nonactivated aldehydes with a Hantzsch ester in the presence of a series of organoboranes: NMR and DFT studies (2019)
  • Author(s): Go Hamasaka, Hiroaki Tsuji, Masahiro Ehara, Yasuhiro Uozumi
  • Journal Title: RSC Adv. Volume: 9 Issue: 18 Pages: 10201-10210
  • DOI: 10.1039/c9ra01468c
  • Peer Reviewed / Open Access
• [Journal Article] Solvent-Free A3 and KA2 Coupling Reactions with mol ppm Level Loadings of a Polymer-Supported Copper(II)-Bipyridine Complex for Green Synthesis of Propargylamines (2019)
  • Author(s): Yan Shuo、Pan Shiguang、Osako Takao、Uozumi Yasuhiro
  • Journal Title: ACS Sustainable Chemistry & Engineering Volume: 7 Issue: 10 Pages: 9097-9102
  • DOI: 10.1021/acssuschemeng.9b01754
  • Peer Reviewed
• [Journal Article] Surface Modification of a Supported Pt Catalyst Using Ionic Liquids for Selective Hydrodeoxygenation of Phenols into Arenes under Mild Conditions (2019)
  • Author(s): Ohta Hidetoshi、Tobayashi Kanako、Kuroo Akihiro、Nakatsuka Mao、Kobayashi Hirokazu、Fukuoka Atsushi、Hamasaka Go、Uozumi Yasuhiro、Murayama Haruno、Tokunaga Makoto、Hayashi Minoru
  • Journal Title: Chemistry European Journal Volume: 25 Issue: 65 Pages: 14762-14766
  • DOI: 10.1002/chem.201902668
  • Peer Reviewed
• [Journal Article] Mechanistic Study on Allylic Arylation in Water with Linear Polystyrene-Stabilized Pd and PdO Nanoparticles (2019)
  • Author(s): Ohtaka Atsushi、Kawase Misa、Usami Akira、Fukui Shiho、Yamashita Mana、Yamaguchi Kazuki、Sakon Akira、Shiraki Tomoya、Ishida Taiki、Nagata Soma、Kimura Yuji、Hamasaka Go、Uozumi Yasuhiro、Shinagawa Tsutomu、Shimomura Osamu、Nomura Ryoki
  • Journal Title: ACS Omega Volume: 4 Issue: 13 Pages: 15764-15770
  • DOI: 10.1021/acsomega.9b02722
  • Peer Reviewed
• [Journal Article] The Hiyama Cross‐Coupling Reaction at Parts Per Million Levels of Pd: In Situ Formation of Highly Active Spirosilicates in Glycol Solvents (2019)
  • Author(s): Ichii Shun、Hamasaka Go、Uozumi Yasuhiro
  • Journal Title: Chemistry Asian Journal Volume: 14 Issue: 21 Pages: 3850-3854
  • DOI: 10.1002/asia.201901155
  • Peer Reviewed / Open Access
• [Journal Article] Arylation of Terminal Alkynes by Aryl Iodides Catalyzed by a Parts-per-Million Loading of Palladium Acetate (2019)
  • Author(s): Hamasaka Go、Roy David、Tazawa Aya、Uozumi Yasuhiro
  • Journal Title: ACS Catalysis Volume: 9 Issue: 12 Pages: 11640-11646
  • DOI: 10.1021/acscatal.9b04593
  • Peer Reviewed
• [Journal Article] Second-Generation meta-Phenolsulfonic Acid-Formaldehyde Resin as a Catalyst for Continuous-Flow Esterification (2019)
  • Author(s): Hu Hao、Ota Hajime、Baek Heeyoel、Shinohara Kenta、Mase Toshiaki、Uozumi Yasuhiro、Yamada Yoichi M. A.
  • Journal Title: Organic Letters Volume: 22 Issue: 1 Pages: 160-163
  • DOI: 10.1021/acs.orglett.9b04084
  • Peer Reviewed
• [Journal Article] Catalytic specificity of linear polystyrene-stabilized Pd nanoparticles during Ullmann coupling reaction in water and the associated mechanism (2018)
  • Author(s): Ohtaka Atsushi、Sakon Akira、Yasui Asuka、Kawaguchi Taira、Hamasaka Go、Uozumi Yasuhiro、Shinagawa Tsutomu、Shimomura Osamu、Nomura Ryoki
  • Journal Title: Journal of Organometallic Chemistry Volume: 854 Pages: 87-93
  • DOI: 10.1016/j.jorganchem.2017.11.016
• [Journal Article] Poly(meta-phenylene oxides) for the design of a tunable, efficient, and reusable catalytic platform (2018)
  • Author(s): Reuben H Hudson, Haoran Zhang, Amy LoTemplio, Georganna Benedetto, Go Hamasaka, Yoichi M. A. Yamada, Jeffrey Louis Katz, Yasuhiro Uozumi
  • Journal Title: Chem. Commun. Volume: 54 Issue: 23 Pages: 2878-2881
  • DOI: 10.1039/c8cc00774h
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Cu-catalyzed reduction of azaarenes and nitroaromatics with diboronic acid as reductant (2018)
  • Author(s): Pi Danwei、Zhou Haifeng、Zhou Yanmei、Liu Qixing、He Renke、Shen Guanshuo、Uozumi Yasuhiro
  • Journal Title: Tetrahedron Volume: 74 Issue: 17 Pages: 2121-2129
  • DOI: 10.1016/j.tet.2018.03.014
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] A Palladium NNC-Pincer Complex as an Efficient Catalyst Precursor for the Mizoroki-Heck Reaction (2018)
  • Author(s): Hamasaka Go、Ichii Shun、Uozumi Yasuhiro
  • Journal Title: Advanced Synthesis & Catalysis Volume: 360 Issue: 9 Pages: 1833-1840
  • DOI: 10.1002/adsc.201800099
  • Peer Reviewed
• [Journal Article] Controlled Aerobic Oxidation of Primary Benzylic Alcohols to Aldehydes Catalyzed by Polymer-Supported Triazine-Based Dendrimer-Copper Composites (2018)
  • Author(s): Uozumi Yasuhiro、Pan Shiguang、Yan Shuo、Osako Takao
  • Journal Title: Synlett Volume: 29 Issue: 09 Pages: 1152-1156
  • DOI: 10.1055/s-0036-1591981
  • Peer Reviewed
• [Journal Article] Aqueous Asymmetric 1,4-Addition of Arylboronic Acids to Enones Catalyzed by an Amphiphilic Resin-Supported Chiral Diene Rhodium Complex under Batch and Continuous-Flow Conditions (2018)
  • Author(s): Shen Guanshuo、Osako Takao、Nagaosa Makoto、Yasuhiro Uozumi
  • Journal Title: J. Org. Chem. Volume: - Issue: 14 Pages: 7380-7387
  • DOI: 10.1021/acs.joc.8b00178
  • Peer Reviewed
• [Journal Article] Poly(tetrafluoroethylene)-Stabilized Metal Nanoparticles: Preparation and Evaluation of Catalytic Activity for Suzuki, Heck, and Arene Hydrogenation in Water (2018)
  • Author(s): Ohtaka Atsushi、Kawase Misa、Aihara Shunichiro、Miyamoto Yasuhiro、Terada Ayaka、Nakamura Kenta、Hamasaka Go、Uozumi Yasuhiro、Shinagawa Tsutomu、Shimomura Osamu、Nomura Ryoki
  • Journal Title: ACS Omega Volume: 3 Issue: 8 Pages: 10066-10073
  • DOI: 10.1021/acsomega.8b01338
  • Peer Reviewed / Open Access
• [Journal Article] Metal-free Reduction of Nitro Aromatics to Amines with B2(OH)4/H2O (2018)
  • Author(s): Zhou Haifeng、Uozumi Yasuhiro、Chen Danyi、Zhou Yanmei、Liu Sensheng、Liu Qixing、Zhang Kaili
  • Journal Title: Synlett Volume: 29 Issue: 13 Pages: 1765-1768
  • DOI: 10.1055/s-0037-1610086
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Asymmetric Copper-Catalyzed C(sp)-H Bond Insertion of Carbenoids Derived from N-Tosylhydrazones (2018)
  • Author(s): Uozumi Yasuhiro、Osako Takao、Nagaosa Makoto、Hamasaka Go
  • Journal Title: Synlett Volume: 29 Issue: 17 Pages: 2251-2256
  • DOI: 10.1055/s-0037-1611003
  • Peer Reviewed
• [Journal Article] Iridium-Catalyzed Direct Cyclization of Aromatic Amines with Diols (2018)
  • Author(s): Minakawa Maki、Watanabe Kouichi、Toyoda Satoru、Uozumi Yasuhiro
  • Journal Title: Synlett Volume: 29 Issue: 18 Pages: 2385-2389
  • DOI: 10.1055/s-0037-1610995
  • Peer Reviewed
• [Journal Article] Preparation of Aryl(dicyclohexyl)phosphines by C-P Bond-Forming Cross-Coupling in Water Catalyzed by an Amphiphilic-Resin-Supported Palladium Complex (2017)
  • Author(s): Uozumi Yasuhiro、Hirai Yoshinori
  • Journal Title: Synlett Volume: 28 Issue: 20 Pages: 2966-2970
  • DOI: 10.1055/s-0036-1590926
  • Peer Reviewed
• [Presentation] Organic molecular transformations in water with amphiphilic resin-supported platinum nanoparticles (2019)
  • Author(s): Yasuhiro Uozumi
  • Organizer: 4th Green Sustainable Conference 2019
  • Int'l Joint Research / Invited
• [Presentation] Organic Reactions in Water with Amphiphilic Polymeric Transition Metal Catalysts (2019)
  • Author(s): Yasuhiro Uozumi
  • Organizer: Thieme Chemistry Workshop
  • Int'l Joint Research / Invited
• [Presentation] NCN Pincer Palladium Complexes:Their Preparation and Reacting Properties (2019)
  • Author(s): Yasuhiro Uozumi
  • Organizer: The 13th International Conference on Heteroatom Chemistry
  • Int'l Joint Research / Invited
• [Presentation] 水中での有機分子変換を実現する高分子固定化触媒の開発 (2019)
  • Author(s): 魚住泰広
  • Organizer: 第124回触媒討論会
  • Invited
• [Presentation] Development of Polymer Supported Catalysts and Their Flow Application (2019)
  • Author(s): Yasuhiro Uozumi
  • Organizer: International Conference on Super Functional Catalysts
  • Int'l Joint Research / Invited
• [Presentation] 「雨宿り効果」に立脚した超機能性固定化触媒の創製 (2018)
  • Author(s): Yasuhiro Uozumi
  • Organizer: 日本プロセス化学会
  • Invited
• [Presentation] Green Organic Transformations in Water with Heterogeneous Catalysts (2018)
  • Author(s): Yasuhiro Uozumi
  • Organizer: IUPAC
  • Int'l Joint Research / Invited
• [Presentation] 化学合成プロセスを変革する超活性固定化触媒 (2018)
  • Author(s): 魚住泰広
  • Organizer: JST
  • Invited
• [Presentation] Recent Development of Flow Reaction Systems with Novel Polymeric Catalysts (2018)
  • Author(s): Yasuhiro Uozumi
  • Organizer: The 4th International Symposium of Middle Molecular Strategy
  • Int'l Joint Research / Invited
• [Book] Pincer Compounds.Chemistry and Applications (2018)
  • Author(s): Y. UOZUMI and G. HAMASAKA
  • Total Pages: 38
  • Publisher: Elsevier
• [Book] Adv. Synth. Catal (2018)
  • Author(s): D. ROY and Y. UOZUMI
  • Total Pages: 23
  • Publisher: Wiley
• [Remarks] 分子科学研究所魚住研究室ホームページ
  • URL: https://groups.ims.ac.jp/organization/uozumi_g/
• [Patent(Industrial Property Rights)] 銀ナノ粒子樹脂複合体及び水素化触媒 (2019)
  • Inventor(s): 魚住泰広、大迫隆男
  • Industrial Property Rights Holder: 大学共同利用機関法人自然科学研究機構
  • Industrial Property Rights Type: 特許
  • Filing Date: 2019