隣接基関与に基づくカルボニル化ならびにカルボキシル化触媒の開発

• Project/Area Number: 21245023
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: The University of Tokyo
• Principal Investigator: 野崎 京子 The University of Tokyo, 工学(系)研究科(研究院), 教授 (60222197)
• Project Period (FY): 2009 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥48,620,000 (Direct Cost: ¥37,400,000、Indirect Cost: ¥11,220,000); Fiscal Year 2011: ¥10,790,000 (Direct Cost: ¥8,300,000、Indirect Cost: ¥2,490,000); Fiscal Year 2010: ¥10,790,000 (Direct Cost: ¥8,300,000、Indirect Cost: ¥2,490,000); Fiscal Year 2009: ¥27,040,000 (Direct Cost: ¥20,800,000、Indirect Cost: ¥6,240,000)
• Keywords: 遷移金属錯体 / 隣接機能部位 / 重合触媒 / 二酸化炭素 / ステレオグラジェントポリマー / 一酸化炭素 / ポリケトン / ステレオグラジエントボリマー

Research Abstract

本研究は、目的の反応の進行を触媒する遷移金属錯体部位(以下、触媒作用部位とよぶ)に対し、その近傍に位置し基質と相互作用することにより反応の効率や選択性の向上などを担う官能基(以下、隣接機能部位とよぶ)を同一分子内に配置させることで、既存の単核金属触媒系では達成できない高効率かつ高選択的な触媒反応を達成することを目的とした。特に二酸化炭素や一酸化炭素を原料とする遷移金属錯体触媒反応に焦点を絞り、研究を進めた。隣接昨日部位としては、本研究開始当初にもちいていたアンモニウム基に着目し、そこにキラリティーを導入した。キラルアンモニウム基の置換位置を種々検討することにより、プロピレンオキシドと二酸化炭素の不斉交互共重合において、得られる脂肪族ポリカルボナートの立体規則性の制御に成功した。すなわち、プロピレンオキシドのラセミ混合物から出発し、一方のエナンチオマーを優先的にポリマー鎖にとりこんだのち、他方のエナンチオマーを続けてこのポリマー鎖にとりこみ続けることで、ステレオグラジエント型のポリカルボナートの合成に成功した。こうして得られたポリカルボナートは、立体制御をおこなっていないポリカルボナートよりも熱安定性が向上していた。熱安定性向上の理由は今のところ不明だが、分子内でステレオコンプレックスなどの特殊な3次元構造が存在している可能性があり、脂肪族ポリカルボナートの物性向上に大きなヒントを与える結果となった。また、一酸化炭素を用いる反応としては、パラジウム触媒を用いるオレフィン類と一酸化炭素の交互共重合において、中心金属に配位しているボスフィン配位子にスルホナート基を結合させた配位子を用いることで、それまで不可能だった汎用極性モノマー(アクリル酸メチルや酢酸ビニル)と一酸化炭素の交互共重合が可能になった。スルホン酸部位が非配位性のアニオンとしての特徴を保ちつつ、静電的な相互作用で触媒作用部位の近傍に位置し、他の配位子の配位を阻害したことが成功の原因である。

Research Products

• [Journal Article] Mechanistic Studies on the Reversible Hydrogenation of Carbon Dioxide Catalyzed by an Ir-PNP Complex (2011)
  • Author(s): R.Tanaka, M.Yamashita, L.W.Chung, K.Morokuma, K.Nozaki
  • Journal Title: Organometallics Volume: 30 Pages: 6742-6750
  • Peer Reviewed
• [Journal Article] Ethylene Polymerization by Palladium/Phosphine-Sulfonate Catalysts in the Presence and Absence of Protic Solvents : Structural and Mechanistic Differences (2011)
  • Author(s): M.Kanazawa, S.Ito, K.Nozaki
  • Journal Title: Organometallics Volume: 30 Pages: 6029-6032
  • Peer Reviewed
• [Journal Article] Tetravalent Metal Complexes as a New Family of Catalysts for Copolymerization of Epoxides with Carbon Dioxide (2011)
  • Author(s): K.Nakano, K.Kobayashi, K.Nozaki
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Pages: 10720-10723
  • Peer Reviewed
• [Journal Article] Pd-Catalyzed Copolymerization of Methyl Acrylate with Carbon Monoxide : Structures, Properties and Mechanistic Aspects toward Ligand Design (2011)
  • Author(s): A.Nakamura, K.Munakata, S.Ito, T.Kochi, L.W.Chung, K.Morokuma, K.Nozaki
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Pages: 6761-6779
  • Peer Reviewed
• [Journal Article] Stereocomplex of Poly(propylene carbonate) : Synthesis of Stereogradient Poly(propylene carbonate) via Stereo- and Enantioselective Copolymerization of Propylene Oxide with Carbon Dioxide (2011)
  • Author(s): K.Nakano, S.Hashimoto, M.Nakamura, T.Kamada, K.Nozaki
  • Journal Title: Angew.Chem.Int.Ed. Volume: 50 Pages: 4868-4871
  • Peer Reviewed
• [Journal Article] Coordination-Insertion Copolymerization of Allyl Monomers with Ethylene (2011)
  • Author(s): S.Ito, M.Kanazawa, K.Munakata, J.-i Kuroda, Y.Okumura, K.Nozaki
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Pages: 1232-1235
  • Peer Reviewed
• [Journal Article] Vinylarene/CO Copolymerization and Vinylarene/Polar Vinyl Monomer/CO Terpolymerization Using Palladium/Phosphine-Sulfonate Catalysts (2011)
  • Author(s): T.Kageyama, S.Ito, K.Nozaki
  • Journal Title: Chem.Asian J. Volume: 6 Pages: 690-697
  • Peer Reviewed
• [Journal Article] Why Did Incorporation of Acrylonitrile to a Linear Polyethylene Become Possible? Comparison of Phosphine-Sulfonate Ligand with Diphosphine and Imine-Phenolate Ligands in the Pd-Catalyzed Ethylene/Acrylonitrile Copolymerization (2010)
  • Author(s): K.Nozaki, S.Kusumoto, S.Noda, T.Kochi, L.W.Chung, K.Morokuma
  • Journal Title: J.Am.Chem.Soc. Volume: 132 Pages: 16030-16042
  • Peer Reviewed
• [Journal Article] Bimetallic mechanism operating in the copolymerization of propylene oxide with carbon dioxide catalyzed by cobalt-salen complexes (2010)
  • Author(s): K.Nakano, S.Hashimoto, K.Nozaki
  • Journal Title: Chem.Sci. Volume: 1 Pages: 369-373
  • Peer Reviewed
• [Journal Article] Reduction of Base-Stabilized Difluoroboranes to Induce Rearrangement Reactions (2010)
  • Author(s): M.Yamashita, Y.Aramaki, K.Nozaki
  • Journal Title: New J.Chem. Volume: 34 Pages: 1774-1782
  • Peer Reviewed
• [Journal Article] A Catalytic Synthesis of Dialkylamines from Alkylamines Using Neopentyl-Substituted PNP Pincer Iridium Complex (2010)
  • Author(s): M.Yamashita, Y.Moroe, T.Yano K.Nozaki
  • Journal Title: Inorg.Chim.Acta Volume: 363(In press)
  • Peer Reviewed
• [Journal Article] Syntheses of PBP Pincer Iridium Complexes : A Supporting Boryl Ligand (2009)
  • Author(s): Y.Segawa, M.Yamashita, K.Nozaki
  • Journal Title: J.Am.Chem.Soc Volume: 131 Pages: 9201-9203
  • Peer Reviewed
• [Journal Article] Group 4 Transition Metal Boryl Complexes : Syntheses, Structures, Boron- Metal Bonding Properties, and Application as a Polymerization Catalyst (2009)
  • Author(s): T.Terabayashi, T.Kajiwara, M.Yamashita, K.Nozaki
  • Journal Title: J.Am.Chem.Soc Volume: 131 Pages: 14162-14163
  • Peer Reviewed
• [Journal Article] Synthesis of N-Heterocyclic Carbene-Sulfonate Palladium Complexes (2009)
  • Author(s): Y.Nagai, T.Kochi, K.Nozaki
  • Journal Title: Organometallics Volume: 28 Pages: 6131-6134
  • Peer Reviewed
• [Journal Article] Diphenylphosphino- or Dicyclohexylphosphino-Tethered Boryl Pincer Ligands : Syntheses of PBP Iridium (III) Complexes and Their Conversion to Iridium- Ethylene Complexes (2009)
  • Author(s): Y.Segawa, M.Yamashita, K.Nozaki
  • Journal Title: Organometallics Volume: 28 Pages: 6234-6242
  • Peer Reviewed
• [Presentation] カルボニル化・カルボキシル化の新触媒開発:どうやって活性な均一系触媒をみつけるか (2012)
  • Author(s): K.Nozaki
  • Organizer: 有機合成2月セミナー有機合成のニュートレンド2012
  • Place of Presentation: エル・おおさか大阪府(招待講演)
  • Year and Date: 2012-02-02
• [Presentation] CO2を原料とするポリマー:合成と構造制御の新展開 (2012)
  • Author(s): K.Nozaki
  • Organizer: 平成23年度東海シンポジウム:精密高分子の拓く未来
  • Place of Presentation: 名古屋国際会議場愛知県(招待講演)
  • Year and Date: 2012-01-13
• [Presentation] New Catalysts for Carbonylation and Carboxylation (2011)
  • Author(s): K.Nozaki
  • Organizer: Mini-Symposium on Organometallics and Catalysis
  • Place of Presentation: Tianjin, China(招待講演)
  • Year and Date: 2011-11-26
• [Presentation] Utilization of CO2 as a Carbon Resource (2011)
  • Author(s): K.Nozaki
  • Organizer: 1st International Symposium on Molecular Activarion
  • Place of Presentation: Hyogo, JAPAN(招待講演)
  • Year and Date: 2011-11-09
• [Presentation] New Catalysts for Carbonylation and Carboxylation (2011)
  • Author(s): K.Nozaki
  • Organizer: 14ACC
  • Place of Presentation: Bangkok, Thailand(招待講演)
  • Year and Date: 2011-09-06
• [Presentation] Rh/Ru Dual Catalyst for the Tandem Hydroformylaton/Hydrogenation Reactions (2011)
  • Author(s): K.Nozaki
  • Organizer: ISPC2011
  • Place of Presentation: kyoto, Japan(基調招待講演)
  • Year and Date: 2011-08-11
• [Presentation] Catalyst Design for Tandem Hydroformylation/Hydrogenation of Alkenes (2011)
  • Author(s): K.Nozaki
  • Organizer: 43rd IUPAC 2011
  • Place of Presentation: San Juan, Puerto Rico(招待講演)
  • Year and Date: 2011-08-05
• [Presentation] Utilization of CO2 as a Carbon Resource (2011)
  • Author(s): K.Nozaki
  • Organizer: FJCCS11
  • Place of Presentation: Rennes, France(招待講演)
  • Year and Date: 2011-07-02
• [Presentation] Catalytic hydrogenation of carbon dioxide using Ir(III)-Pincer Complexes (2011)
  • Author(s): K.Nozaki
  • Organizer: ICCDU XI
  • Place of Presentation: Dijon, France(招待講演)
  • Year and Date: 2011-06-28
• [Presentation] Group 10 metal catalyzed copolymerization of ethylene with polar monomers (2011)
  • Author(s): K.Nozaki
  • Organizer: FAPS-PC2011
  • Place of Presentation: Beijing, CHINA(招待講演)
  • Year and Date: 2011-05-10
• [Presentation] Boron nucleophiles in organic synthesis (2011)
  • Author(s): K.Nozaki
  • Organizer: ACS 241st National Meeting Acceptance
  • Place of Presentation: Anaheim, California, USA(招待講演)
  • Year and Date: 2011-03-29
• [Presentation] Tandem hydroformylation/hydrogenation of terminal olefins (2011)
  • Author(s): K.Nozaki
  • Organizer: ACS 241st National Meeting Acceptance
  • Place of Presentation: Anaheim, California, USA(招待講演)
  • Year and Date: 2011-03-27
• [Presentation] New Catalyst Systems for Carbonylation and Carboxylation (2010)
  • Author(s): K.Nozaki
  • Organizer: PACIFICHEM2010
  • Place of Presentation: Hawaii Convention Center, USA(招待講演)
  • Year and Date: 2010-12-17
• [Presentation] New Catalyst Systems for Carbonylation and Carboxylation (2010)
  • Author(s): K.Nozaki
  • Organizer: Bristol-Myers Squibb Symposium
  • Place of Presentation: University of Michigan, USA(招待講演)
  • Year and Date: 2010-12-03
• [Presentation] Matal-Catalyzed Coordination-Insertion Polymerization of Polar Monomers (2010)
  • Author(s): K.Nozaki
  • Organizer: BCH Seminar
  • Place of Presentation: City University of Hong Kong, Kawloon Tone HONGKONG(招待講演)
  • Year and Date: 2010-10-20
• [Presentation] Structural Control in Polymerization Utilizing CO or CO2 (2010)
  • Author(s): K.Nozaki
  • Organizer: 18th Gordon Research Conference Stereochemistry
  • Place of Presentation: Salve Regina University Newport, RI, USA(招待講演)
  • Year and Date: 2010-08-02
• [Presentation] UTILIZATION OF CARBON DIOXIDE AS A CAEBON RESOURCE (2010)
  • Author(s): K.Nozaki
  • Organizer: BOSSXII (12th Belgian Organic Synthesis Symposium)
  • Place of Presentation: University of Namur (FUNDP), Namur, Belgium(招待講演)
  • Year and Date: 2010-07-15
• [Presentation] Metal-Catakyzed Coordination-Insertion Polymerization of Polar Monomers (2010)
  • Author(s): K.Nozaki
  • Organizer: ISHC-17 (International Symposium on Homogeneous Catalysis)
  • Place of Presentation: Poznan, Poland(基調招待公演)
  • Year and Date: 2010-07-08
• [Presentation] Coordination Polymerization of Polar Monomers (2010)
  • Author(s): K.Nozaki
  • Organizer: 2nd International Symposium on Polymer Materials Science and Technology
  • Place of Presentation: Harbin Engineering University, Harbin, Chine(招待講演)
  • Year and Date: 2010-05-31
• [Presentation] 一酸化炭素、二酸化炭素をモノマーとする高分子合成 (2010)
  • Author(s): 野崎京子
  • Organizer: 10-1ポリマーフロンティア21炭素循環型社会に貢献する高分子科学・産業
  • Place of Presentation: 東工大蔵前会館東京都(招待講演)
  • Year and Date: 2010-04-09
• [Presentation] Coordination Polymerization of Polar Monomers (2009)
  • Author(s): K.Nozaki
  • Organizer: Heidelberg Forum of Molecular Catalysis
  • Place of Presentation: Univ.of Heidelberg Germany
  • Year and Date: 2009-11-06
• [Presentation] Homogeneous catalysis for controlled polymerization of polar monomers (2009)
  • Author(s): K.Nozaki
  • Organizer: GRATAMA WORKSHOP 2009
  • Place of Presentation: Delft University of Technology, Nederland
  • Year and Date: 2009-09-19
• [Presentation] Carbon Monoxide and Carbon Dioxide as a C1 Synthon in Organic Synthesis (2009)
  • Author(s): K.Nozaki
  • Organizer: Gordon Research Conferences
  • Place of Presentation: Tilton, NH, USA
  • Year and Date: 2009-07-29
• [Patent(Industrial Property Rights)] 耐熱安定性に優れたポリカーボネートおよびその製造方法 (2011)
  • Inventor(s): 中野幸司・野崎京子・西岡聖司・藤本信貴
  • Industrial Property Rights Holder: 国立大学法人東京大学・住友精化株式会社
  • Industrial Property Number: 2011-016798
  • Filing Date: 2011-01-28
• [Patent(Industrial Property Rights)] コバルトーケトイミナト錯体,および当該錯体を用いたボリカルボナートの製造方法 (2010)
  • Inventor(s): 中野幸司・野崎京子・西岡聖司・山田徹・菊地哲・岡田敦
  • Industrial Property Rights Holder: 国立大学法人東京大学・学校法人慶應義塾
  • Industrial Property Number: 2010-014562
  • Filing Date: 2010-01-26
• [Patent(Industrial Property Rights)] ボリカルボナート重合触媒の回収方法 (2010)
  • Inventor(s): 中野幸司・野崎京子・西岡聖司
  • Industrial Property Rights Holder: 国立大学法人東京大学
  • Industrial Property Number: 2010-061295
  • Filing Date: 2010-03-17
• [Patent(Industrial Property Rights)] 二核金属錯体,および当該二核金属錯体を用いたポリカルボナートの製造方法 (2010)
  • Inventor(s): 中野幸司・野崎京子
  • Industrial Property Rights Holder: 国立大学法人東京大学
  • Industrial Property Number: 2010-061342
  • Filing Date: 2010-03-17
• [Patent(Industrial Property Rights)] 金属錯体を用いたボリカルボナートの製造方法,金属錯体,および金属錯体を含む触媒システム (2010)
  • Inventor(s): 中野幸司・野崎京子・杉本裕
  • Industrial Property Rights Holder: 国立大学法人東京大学・株式会社東京大学TLO
  • Industrial Property Number: 2010-061368
  • Filing Date: 2010-03-17
• [Patent(Industrial Property Rights)] コバルト錯体,当該錯体を含む触媒システム,及び当該錯体を用いたエボキシド化合物と二酸化炭素の共重合方法 (2009)
  • Inventor(s): 中野幸司・野崎京子・西岡聖司
  • Industrial Property Rights Holder: 国立大学法人東京大学
  • Industrial Property Number: 2009-125458
  • Filing Date: 2009-05-25