貴金属・シリカ被覆磁性マイクロ粒子担持触媒の開発

• Project/Area Number: 20037028
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Nagoya University
• Principal Investigator: 北村 雅人 Nagoya University, 物質科学国際研究センター, 教授 (50169885)
• Project Period (FY): 2008 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥3,800,000 (Direct Cost: ¥3,800,000); Fiscal Year 2009: ¥1,900,000 (Direct Cost: ¥1,900,000); Fiscal Year 2008: ¥1,900,000 (Direct Cost: ¥1,900,000)
• Keywords: 不均-触媒 / 磁性粒子 / アリル保護基 / ルテニウム / πアリル錯体 / 不均一触媒

Research Abstract

CpRu(IV)(η^3-C_3H_5)(2-ピリジンカルボキシラト)触媒は、メタノール中アリルエーテルやアリルエステル結合を切断できる。共生成物は低沸点のアリルメチルエーテルのみであり、濃縮のみで最終生成物を単離できる操作性の高い手法として「保護基の化学」の観点から注目を集めている。残る問題は触媒と生成物との分離であり、如何に触媒を除くかは有機合成効率の高低に大きく影響する。この状況を鑑み、日立マクスウェル社の協力を得、「高分散性・低保磁力・高飽和磁化率」を特徴とする球形マイクロFe_3O_4@SiO_2粒子を調製し、この粒子に上記触媒を固定化した新型の不均一系触媒を開発した。通常の磁石を用いるだけで、迅速に触媒を分離し、凝集することなく容易に再分散させることができる。分配による単離が容易でないオリゴリボヌクレオチド類やペプチド類の最終脱保護に有効であり、簡単な操作で定量的に目的物を単離できた。
本触媒において2-ピリジンカルボン酸配位子部の立体的・電子的・軌道的変化が反応活性に与える影響は大きい。触媒活性発現機構に対する理解をより深めるべく、最も単純な2-ピリジンカルボン酸を基準として、アリル2-フェニルエチルエーテルの脱アリル化における4位置換基効果をハメットプロットした。その結果、およそ二つの領域で異なる直線性が得られ、反応律速であるアルコールの求核攻撃を有利とする配位子の「π電子受容性」とドナー・アクセプター二官能性触媒発現のためのカルボン酸部の「酸性度」との適切なバランスが重要な役割を演じていることを示した。

Research Products

• [Journal Article] Asymmetric Dehydrative Cyclization of co-Hydroxy Allyl Alcohols Catalyzed by Ruthenium Complexes (2009)
  • Author(s): S.Tanaka, T.Seki, M.Kitamura
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 8948-8951
  • Peer Reviewed
• [Journal Article] Solid-phase Synthesis of Protected a-Amino Phosphonic Acid Oligomers (2009)
  • Author(s): Y.Ishibashi, M.Kitamura
  • Journal Title: Chem.Commun. 45 Pages: 6985-6987
  • Peer Reviewed
• [Journal Article] A Magnetically Separable Heterogeneous Deallylation Catalyst : [CpRu(η^3-C_3H_5)(2-pyridinecarboxylato)]PF_6 Complex Supported-on a Ferromagnetic Microsize Particle Fe_3O_4@SiO_2 (2009)
  • Author(s): T.Hirakawa, S.Tanaka, N.Usuki, H.Kanzaki, M.Kishimoto, M.Kitamura
  • Journal Title: Eur.J.Org.Chem. 6 Pages: 789-792
  • Peer Reviewed
• [Journal Article] Dehydrative Allylation of Alcohols and Deallylation of Allyl Ethers Catalyzed by [CpRu(CH_3CN)_3]PF_6 and 2-pyridinecarboxylic Acid Derivatives. Effect of π-accepting Ability and COOH Acidity of Ligand on Reactivity (2009)
  • Author(s): S.Tanaka, H.Saburi, T.Hirakawa, T.Seki, M.Kitamura
  • Journal Title: Chem.Lett. 38 Pages: 188-189
  • NAID: 10025119541
  • Peer Reviewed
• [Journal Article] A Magnetically Separable Heterogeneous Deallylation Catalyst : [CpRu(n^3-C_3H_5)(2-pyridinecarboxylato)]PF_6 Complex Supported on a Ferromagnetic Microsize Particle Fe_3O_4@SiO_2 (2009)
  • Author(s): T. Hirakawa, S. Tanaka, N. Usuki, H. Kanzaki, M. Kishimoto, and M. Kitamura
  • Journal Title: Eur. J. Org. Chem. 6 Pages: 789-792
  • Peer Reviewed
• [Journal Article] Dehydrative Allylation of Alcohols and Deallylation of Allyl Ethers Catalyzed by [CpRu(CH_3CN)_3] PF_6 and 2-pyridinecarboxylic Acid Derivatives. Effect of p-accepting Ability and COOH. Acidity of Ligand on Reactivity (2009)
  • Author(s): S. Tanaka, H. Saburi, T. Hirakawa, T. Seki, and M. Kitamura
  • Journal Title: Chem. Lett. 38 Pages: 188-189
  • Peer Reviewed
• [Journal Article] Solvent-free One-pot Synthesis of Thallium Complexes of Tp [BH(Pz)_3]-(Pz=pyrazolate) and its Derivatives (2008)
  • Author(s): K. Tsuda, K. Miyata, T. Okuno, M. Yoshimura, S. Tanaka, and M. Kitamura
  • Journal Title: Tetrahedron Lett. 49 Pages: 2990-2993
  • Peer Reviewed
• [Journal Article] A New, Efficient and Direct Preparation of TlTp and Related Complexes with TlBH_4 (2008)
  • Author(s): M. Kitamura, Y. Takenaka, T. Okuno, R. Holl, and B. Wtinsch
  • Journal Title: Eur. J. Inorg. Chem. 7 Pages: 1182-1192
  • Peer Reviewed
• [Journal Article] Synthesis of 2, 5-Diazabicyclo [2. 2. 2] octanes by Dieckmann Analogous Cyclization (2008)
  • Author(s): R. Holl, M. Dykstra, M. Schneiders, R. Froehlich, M. Kitamura, E. U. Wuerthwein, and B. Wunsch
  • Journal Title: Aust. J. Chem. 61 Pages: 914-919
  • Peer Reviewed
• [Journal Article] 不斉水素化と医薬品合成 (2008)
  • Author(s): 吉村正宏, 北村雅人
  • Journal Title: 綜合臨床 57 Pages: 125-131
• [Presentation] NNP型三座配位子BINAN-Py-PPh_2-不斉水素化Ru錯体触媒におけるDMSO効果- (2010)
  • Author(s): 中塚宏志、田中慎二、北村雅人
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: Osaka
  • Year and Date: 2010-03-26
• [Presentation] ω-ヒドロキシアリルアルコール類の触媒的不斉環化 (2010)
  • Author(s): 関知昭、田中慎二、北村雅人
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: Osaka
  • Year and Date: 2010-03-26
• [Presentation] ω-ヒドロキシアリルアルコール類の触媒的不斉環化 (2010)
  • Author(s): 北村雅人
  • Organizer: 特定領域研究「協奏機能触媒」第7回公開シンポジウム
  • Place of Presentation: Tokyo
  • Year and Date: 2010-03-05
• [Presentation] A New sp^2N-Based Bidentate Ligand Naph-diPIMand the Behavior of Metal Complexes (2010)
  • Author(s): Kengo Miyata, Hironori Kutsuna, Masato Kitamura
  • Organizer: 平田メモリアルレクチャー
  • Place of Presentation: Nagoya
  • Year and Date: 2010-01-12
• [Presentation] (9H-Fluoren-9-yl)methanesulfonyl (Fms) Amino-Protecting Group : A New Complementary to Fmoc Function (2010)
  • Author(s): Yoshitaka Ishibashi, Masato Kitamura
  • Organizer: 平田メモリアルレクチャー
  • Place of Presentation: Nagoya
  • Year and Date: 2010-01-12
• [Presentation] A NNP-type Tridentate Ligand-DMSO Effect on Asymmetric Hydrogenation by of Ru Catalyst- (2010)
  • Author(s): Hiroshi Nakatsuka, Shinji Tanaka, Masato Kitamura
  • Organizer: The 3rd International Conference on Joint Project of Chemical Synthesis Core Research Institutions
  • Place of Presentation: Nagoya
  • Year and Date: 2010-01-07
• [Presentation] Catalytic Asymmetric Dehydrative Cyclization of ω-Hydroxy Allyl Alcohols (2010)
  • Author(s): Tomoaki Seki, Shinji Tanaka, Masato Kitamura
  • Organizer: The 3rd International Conference on Joint Project of Chemical Synthesis Core Research Institutions
  • Place of Presentation: Nagoya
  • Year and Date: 2010-01-07
• [Presentation] Catalytic Asymmetric Dehydrative Cyclization of ω-Hydroxy Allyl Alcohols (2009)
  • Author(s): Tomoaki Seki, Shinji Tanaka, Masato Kitamura
  • Organizer: International Symposium on Catalysis and Fine Chemicals
  • Place of Presentation: Seoul
  • Year and Date: 2009-12-17
• [Presentation] Fe_3O_4@SiO_2-L-CpRu : A Magnetically Separable Heterogeneous Deallylation Catalyst (2009)
  • Author(s): Shinji Tanaka, Tomoaki Seki, Prasun Kanti Pradhan, Hiroshi Nakatsuka, Masato Kitamura
  • Organizer: International Symposium on Catalysis and Fine Chemicals
  • Place of Presentation: Seoul
  • Year and Date: 2009-12-17
• [Presentation] Donor-Acceptor Bifunctional Catalyst (DACat) From DAIB-Zn to Ph-BINAN-H-Py-Ru and CpRuAllQA (2009)
  • Author(s): Masato Kitamura
  • Organizer: International Symposium on Catalysis and Fine Chemicals
  • Place of Presentation: Seoul
  • Year and Date: 2009-12-16
• [Presentation] sp^2窒素系二座配位子Naph-diPIM-金属錯体の合成およびその触媒機能 (2009)
  • Author(s): 宮田健吾、沓名洋典、北村雅人
  • Organizer: 第三回物質科学フロンティアセミナー
  • Place of Presentation: Nagoya
  • Year and Date: 2009-11-30
• [Presentation] ω-ヒドロキシアリルアルコール類の触媒的不斉環化 (2009)
  • Author(s): 関知昭、田中慎二、北村雅人
  • Organizer: 第3回物質科学フロンティアセミナー
  • Place of Presentation: Nagoya
  • Year and Date: 2009-11-30
• [Presentation] BINAN-Py-PPh_2, A NNP-type Tridentate Ligand-DMSO Effect on Asymmetric Hydrogenation by Use of Ru Catalyst- (2009)
  • Author(s): Hiroshi Nakatsuka, Shinji Tanaka, Masato Kitamura
  • Organizer: 第5回物質合成シンポジウム
  • Place of Presentation: Nagoya
  • Year and Date: 2009-11-19
• [Presentation] NNP型三座配位子BINAN-Py-PPh_2-不斉水素化Ru錯体触媒におけるDMSO効果- (2009)
  • Author(s): 中塚宏志、田中慎二、北村雅人
  • Organizer: 第40回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: Gifu
  • Year and Date: 2009-11-08
• [Presentation] ω-ヒドロキシアリルアルコール類の触媒的不斉環化 (2009)
  • Author(s): 関知昭、田中慎二、北村雅人
  • Organizer: 第40回中部化学関係単協会支部連合秋季大会
  • Place of Presentation: Gifu
  • Year and Date: 2009-11-08
• [Presentation] ドナー・アクセプター二官能性触媒-環境調和型有機合成法の開拓に向けて- (2009)
  • Author(s): 北村雅人
  • Organizer: 第40回中部化学関係学協会支部連合秋季大会特別討論会「環境負荷低減を指向した有機合成」
  • Place of Presentation: 岐阜
  • Year and Date: 2009-11-07
• [Presentation] NNP型三座配位子BINAN-Py-PPh_2-不斉水素化Ru錯体触媒におけるDMSO効果- (2009)
  • Author(s): 中塚宏志、田中慎二、北村雅人
  • Organizer: 第三回物質科学プロンティアセミナー
  • Place of Presentation: Nagoya
  • Year and Date: 2009-11-04
• [Presentation] Donor-Acceptor Bifunctional Catalyst (2009)
  • Author(s): Masato Kitamura
  • Organizer: The 14th Japan-Korea Seminar on Organic Chemistry
  • Place of Presentation: 熱海
  • Year and Date: 2009-10-23
• [Presentation] BINAN-Py-PPh_2, A NNP-type Tridentate Ligand -DMSO Effect on Asymmetric Hydrogenation by Use of Ru Catalvst- (2009)
  • Author(s): Hiroshi Nakatsuka, Shinji Tanaka, Masato Kitamura
  • Organizer: 第8回日独共同セミナー
  • Place of Presentation: Nagoya
  • Year and Date: 2009-09-28
• [Presentation] Redox-involved Donor-Acceptor Bifunctional Catalyst (RDACat) -Mechanism of Allyloxy C-O Bond Activation by [CpRu(CH_3CN)_3]PF_6/2-Pyridinecarboxylic Acid Combined Svstem- (2009)
  • Author(s): Shinji Tanaka, Tomoaki Seki, Masato Kitamura
  • Organizer: 特定領域研究「協奏機能触媒」第4回国際シンポジウム
  • Place of Presentation: Sapporo
  • Year and Date: 2009-08-28
• [Presentation] Desymmetric Hydrogenation of a moso-Cyclic Anhydride toward Biotin Synthesis (2009)
  • Author(s): Kazuomi Tsuda, Hiroshi Nakatsuka, Masahiro Yoshimura, Masato Kitamura
  • Organizer: Nagoya University Global COE in Chemistry 2nd Annual Symposium
  • Place of Presentation: Nagoya
  • Year and Date: 2009-06-07
• [Presentation] A Magnetically Separable Heterogeneous Deallylation Catalyst : [CpRu(η^3-C_3H_5)(2-pyridinecarboxylato)]PF_6 Complex Supported on a Ferromagnetic Microsize Particle Fe_3O_4@SiO_2 (2009)
  • Author(s): Takuya Hirakawa, Tomoaki Seki, Shinji Tanaka, Masato Kitamura
  • Organizer: Nagoya University Global COE in Chemistry 2nd Annual Symposium
  • Place of Presentation: Nagoya
  • Year and Date: 2009-06-07
• [Presentation] Practical Synthesis of A New sp^2N-Based Bidentate Leaand Naph-diPIM and the Behavior of its Metal Complexes (2009)
  • Author(s): Kengo Miyata, Hironori Kutsuna, Yoshitaka Ishibashi, Masato Kitamura
  • Organizer: Nagoya University Global COE in Chemistry 2nd Annual Symposium
  • Place of Presentation: Nagoya
  • Year and Date: 2009-06-07
• [Presentation] A Magnetically Separable Heterogeneous Deallylation Catalyst : [CpRu(η^3-C_3H_5)(2-piridinecarboxylato)]PF_6 Complex Supported on a Ferromagnetic Microsize Particle Fe_3O_4@SiO_2 (2009)
  • Author(s): Takuya Hirakawa, Shinji Tanaka, Masato Kitamura
  • Organizer: 7th joint IRTG Symposium
  • Place of Presentation: Munster
  • Year and Date: 2009-05-02
• [Presentation] Goodwin-Lions型sp^2N/sp^3N混合系配位子Ph-BINAN-H-Py-ルテニウム錯体の不斉水素化機能- (2009)
  • Author(s): Masato Kitamura
  • Organizer: 第4回物質合成シンポジウム「合成化学とナノ科学の接点」
  • Place of Presentation: 名古屋
  • Year and Date: 2009-01-23
• [Presentation] Goodwin-Lions型錯体触媒を用いるケトン類の不斉水素化 (2008)
  • Author(s): 北村雅人
  • Organizer: 特定領域研究「炭素資源の高度分子変換」第六回公開シンポジウム
  • Place of Presentation: 金沢
  • Year and Date: 2008-12-04
• [Presentation] Origin of the Minor Enantiomeric Product in NOYORI Olefin Hydrogenation (2008)
  • Author(s): Masato Kitamura
  • Organizer: The 5th joint IRTG SYMPOSIUM between Nagoya University and University of Mruzster
  • Place of Presentation: Minster, Germany
  • Year and Date: 2008-04-30
• [Book] Reduction by Homogenous Catalysis or Biocatalysis in Science of Synthesis, Houben-Weyl Methods of Molecular Transformations (2009)
  • Author(s): M.Tsukamoto, M.Kitamura
  • Publisher: Georg Thieme Verlag
• [Book] Synthesis by Substitution in Science of Synthesis, Houben-Weyl Methods of Molecular Transformations(Vol. 37 Ethers, Chapter 37. 1. 2) (2008)
  • Author(s): M. Tsukamoto, and M. Kitamura
  • Publisher: Georg Thieme Verlag
• [Patent(Industrial Property Rights)] 不斉合成触媒用配位子、及びそれを用いたα-アルケニル環状工ーテル類の製造方法 (2009)
  • Inventor(s): 北村雅人, 田中慎二
  • Industrial Property Number: 2009-233813
  • Filing Date: 2009-10-07