Development of Catalytic Systems for C-C Bond-Forming Reactions in Aqueous Media

• Project/Area Number: 17065004
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: The Institute of Physical and Chemical Research
• Principal Investigator: MANABE Kei The Institute of Physical and Chemical Research, 眞鍋独立主幹研究ユニット, 独立主幹研究員 (00251439)
• Project Period (FY): 2005 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥17,100,000 (Direct Cost: ¥17,100,000); Fiscal Year 2008: ¥4,900,000 (Direct Cost: ¥4,900,000); Fiscal Year 2007: ¥4,900,000 (Direct Cost: ¥4,900,000); Fiscal Year 2006: ¥4,900,000 (Direct Cost: ¥4,900,000); Fiscal Year 2005: ¥2,400,000 (Direct Cost: ¥2,400,000)
• Keywords: 人工酵素 / パラジウム / クロスカップリング / オリゴアレーン / 触媒 / 位置選択的反応 / 遷移金属 / グリニャール試薬 / ヒドロキシフェニルボロン酸 / 二段階繰り返し合成法 / ピナコールエステル / 鈴木カップリング / 根岸カップリング / 水系媒体 / 鈴木-宮浦クロスカップリング / ボロン酸 / ホスフィン / Lewis酸

Research Abstract

本研究は、有用物質の効率的化学合成法の開発を目指すものである。水溶液中で有効に機能する触媒の開発を最終目標として、触媒活性部位と基質結合部位とを合わせ持つオリゴアレーン型触媒の開発研究を行った。その結果、以下の3つの研究成果を得た。(1)オリゴアレーン類の効率的合成法として、二段階繰り返し合成法を開発した。(2)新規オリゴアレーン型触媒として、オリゴアレーン型ホスフィンとパラジウムとを組み合わせた触媒を開発した。(3)他の触媒を用いる位置選択的クロスカップリング反応の新法を開発した。これらの反応により、種々のベンゼン誘導体の効率的合成が可能となる。

Research Products

• [Journal Article] High Ortho Preference in Ni-Catalyzed Cross-Coupling of Halophenols with Alkyl Grignard Reagents (2009)
  • Author(s): Wang, J.-R., Manabe, K.
  • Journal Title: Org. Lett. 11 Pages: 741-744
  • Peer Reviewed
• [Journal Article] High Ortho Preference in Ni-Catalyzed Cross-Coupling of Halophenols with Alkyl Grignard Reagents (2009)
  • Author(s): Wang, J. -R.
  • Journal Title: Organic Letters 11 Pages: 741-744
  • Peer Reviewed
• [Journal Article] Synthesis of Substituted Monohalobenzenes via Ortho-Selective Cross-Coupling of Dihalobenzenes with Electron-Donating Ortho-Directing Groups (2008)
  • Author(s): Ishikawa, S., Manabe, K.
  • Journal Title: Synthesis Pages: 3180-3182
  • Peer Reviewed
• [Journal Article] Ortho-Selective Cross-Coupling of Fluorobenzenes with Grignard Reagents. Acceleration by Electron-Donating Ortho-Directing Groups (2008)
  • Author(s): Manabe, K., Ishikawa, S.
  • Journal Title: Synthesis Pages: 2645-2649
  • Peer Reviewed
• [Journal Article] Oligoarenes as Molecular Backbones of Catalysts : Synthesis and Applications (2008)
  • Author(s): Manabe, K., Ishikawa, S.
  • Journal Title: Chem. Commun. Pages: 3829-3838
  • Peer Reviewed
• [Journal Article] Synthesis of Substituted Monohalobenzenes via Ortho-Selective Cross-Coupling of Dihalobenzenes with Electron-Donating Ortho-Directing Groups (2008)
  • Author(s): Ishikawa, S.
  • Journal Title: Synthesis Pages: 3180-3182
  • Peer Reviewed
• [Journal Article] Ortho-Selective Cross-Coupling of Fluorobenzenes with Grignard Reagents. Acceleration by Electron-Donating Ortho-Directing Groups (2008)
  • Author(s): Manabe, K.
  • Journal Title: Synthesis Pages: 2645-2649
  • Peer Reviewed
• [Journal Article] Oligoarenes as Molecular Backbones of Catalysts : Synthesis and Applications (2008)
  • Author(s): Manabe, K.
  • Journal Title: Chemical Communications Pages: 3829-3838
  • Peer Reviewed
• [Journal Article] Highly Ortho-Selective Cross Coupling of Dichlorobenzene Derivatives with Grignard Reagents (2007)
  • Author(s): Ishikawa, S., Manabe, K.
  • Journal Title: Org. Lett. 9 Pages: 5593-5595
  • Peer Reviewed
• [Journal Article] ortho-Selective Cross Coupling of Dibromophenols and Dibromoanilines with Grignard Reagents in the Presence of Palladium Catalysts Bearing Hydroxylated Oligoarene-type Phosphine (2007)
  • Author(s): Ishikawa, S., Manabe, K.
  • Journal Title: Chem. Lett. 36 Pages: 1304-1305
  • NAID: 10019791922
  • Peer Reviewed
• [Journal Article] Oligoarene Strategy for Catalyst Development. Hydroxylated Oligoarene-type Phosphines for Palladium-catalyzed Cross Coupling (2007)
  • Author(s): Ishikawa, S., Manabe, K.
  • Journal Title: Chem. Lett. 36 Pages: 1302-1303
  • NAID: 10019791898
  • Peer Reviewed
• [Journal Article] Highly Ortho-Selective Cross-Coupling of Dichlorobenzene Derivatives with Grignard Reagents (2007)
  • Author(s): Ishikawa, S.
  • Journal Title: Organic Letters 9 Pages: 5593-5595
  • Peer Reviewed
• [Journal Article] Ortho-Selective Cross Coupling of Dibromophenols and Dibromoanilines with Grignard Reagents in the Presence of Palladium Cataysts Bearing Hydroxylated Oligoarene-type Phosphine (2007)
  • Author(s): Ishikawa, S.
  • Journal Title: Chemistry Letters 36 Pages: 1304-1305
  • Peer Reviewed
• [Journal Article] Oligoarene Strategy for Catalyst Development. Hydroxylated Oligoarene-type Phosphines for Palladium-catalyzed Cross Coupling (2007)
  • Author(s): Ishikawa, S.
  • Journal Title: Chemistry Letters 36 Pages: 1302-1303
  • Peer Reviewed
• [Journal Article] Negishi Coupling Strategy of a Repetitive Two-Step Method for Oligoarene Synthesis (2006)
  • Author(s): Shimizu, H., Manabe, K.
  • Journal Title: Tetrahedron Lett. 47 Pages: 5927-5931
  • Peer Reviewed
• [Journal Article] Synthetic Method for Multifunctionalized Oligoarenes Using Pinacol Esters of Hydroxyphenylboronic Acids (2006)
  • Author(s): Ishikawa, S., Manabe, K.
  • Journal Title: Chem. Commun. Pages: 2589-2591
  • Peer Reviewed
• [Journal Article] Repetitive Two-Step Method for Oligoarene Synthesis through Rapid Cross-Coupling of Hydroxyphenylboronic Acids and Anhydrides (2006)
  • Author(s): Ishikawa, S., Manabe, K.
  • Journal Title: Chem. Lett. 35 Pages: 164-165
  • NAID: 10017166795
  • Peer Reviewed
• [Journal Article] Synthetic Method for Multifunctionalized Oligoarenes Using Pinacol Esters of Hydroxyphenylboronic Acids (2006)
  • Author(s): Ishikawa, S
  • Journal Title: Chemical Communications Pages: 2589-2591
• [Journal Article] Negishi Coupling Strategy of a Repetitive Two-Step Method for Oligoarene Synthesis (2006)
  • Author(s): Shimizu, H.
  • Journal Title: Tetrahedron Letters 47 Pages: 5927-5931
• [Journal Article] Repetitive Two-Step Method for Oligoarene Synthesis through Rapid Cross-Coupling of Hydroxyphenylboronic Acids and Anhydrides (2006)
  • Author(s): Ishikawa, S., Manabe, K.
  • Journal Title: Chemistry Letters 35 Pages: 164-165
  • NAID: 10017166795
• [Presentation] Pd-Catalyzed Ortho-Selective Cross-Coupling of Dihalobenzenes with Grignard Reagents (2009)
  • Author(s): Manabe, K.
  • Organizer: Second Japan-Singapore Bilateral Symposium on Catalysis
  • Place of Presentation: 京都
  • Year and Date: 2009-01-06
• [Presentation] Ni-Catalyzed Ortho-Selective Cross-Coupling of Dihalophenols with Alkyl Grignard Reagents at Room Temperature (2009)
  • Author(s): 王嘉瑞, 眞鍋敬
  • Organizer: 日本薬学会第129年会
  • Place of Presentation: 京都
• [Presentation] オリゴアレーン型ホスフィンを用いる位置選択的クロスカップリングの開発 (2009)
  • Author(s): 石川俊平, 眞鍋敬
  • Organizer: 日本薬学会第129年会
  • Place of Presentation: 京都
• [Presentation] Pd-Catalyzed Ortho-Selective Cross-Coupling of Dihalobenzenes with Grignard Reagents (2009)
  • Author(s): Kei Manabe
  • Organizer: Second Japan-Singapore Bilateral Symposium on Catalysis
  • Place of Presentation: Kyoto
• [Presentation] Ni-Catalyzed Ortho-Selective Gross-Coupling of Dihalophenols with Alkyl Grignard Reagents at Room Temperature (2009)
  • Author(s): 王 嘉瑞
  • Organizer: 日本薬学会第129年会
  • Place of Presentation: 京都
• [Presentation] オリゴアレーンを骨格とする人工酵素型触媒の開発研究 (2008)
  • Author(s): 眞鍋敬
  • Organizer: 特定領域研究「炭素資源の高度分子変換」第6回公開シンポジウム
  • Place of Presentation: 金沢
• [Presentation] 疎水性基質結合部位を持つオリゴアレーン型二核ロジウム触媒の開発研究 (2008)
  • Author(s): 蔡貞廈, 清水春佳, 眞鍋敬
  • Organizer: 第34回反応と合成の進歩シンポジウム
  • Place of Presentation: 京都
• [Presentation] Ortho-Selective Cross-Coupling of Dihalobenzene Derivatives (2008)
  • Author(s): Shunpei Ishikawa, Kei Manabe
  • Organizer: The First International Symposium on Process Chemistry (ISPC 08)
  • Place of Presentation: Kyoto
• [Presentation] 水酸基含有ホスフィン-パラジウム触媒を用いるオルト選択的クロスカップリングの開発 (2008)
  • Author(s): 石川俊平, 眞鍋敬
  • Organizer: 日本薬学会第128年会
  • Place of Presentation: 横浜
• [Presentation] Ortho-Selective Cross-Coupling of Dihalobenzene Derivatives (2008)
  • Author(s): Ishikawa, S.
  • Organizer: The First International Symposium on Process Chemistry (ISPC 08)
  • Place of Presentation: 京都
• [Presentation] 精密有機合成に役立つ触媒をオリゴアレーン型分子でつくる (2007)
  • Author(s): 眞鍋敬
  • Organizer: 理研シンポジウム 第8回 分析・解析技術と化学の最先端
  • Place of Presentation: 理研和光キャンパス
  • Year and Date: 2007-12-11
• [Presentation] Ortho-Selective Cross Coupling with Grignard Reagents in the Presence of Palladium Catalysts Bearing Hydroxylated Oligoarene-Type Phosphines (2007)
  • Author(s): Shunpei Ishikawa, Kei Manabe
  • Organizer: 2007 Workshop on Organometallic Chemistry
  • Place of Presentation: Wako
• [Presentation] ヒドロキシル基含有オリゴアレーン型ホスフィンの開発と、位置特異的および位置選択的クロスカップリングへの展開 (2007)
  • Author(s): 石川俊平, 眞鍋敬
  • Organizer: 第92回有機合成シンポジウム
  • Place of Presentation: 早稲田大学
• [Presentation] Pd-Catalyzed Site-Selective Cross-Coupling of Dibromophenols with Grignard Reagents Using Oligoarene-Type Phosphine Ligands (2007)
  • Author(s): Shunpei Ishikawa, Kei Manabe
  • Organizer: 14th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 14)
  • Place of Presentation: Nara
• [Presentation] Hydroxylated Oligoarene-Type Phosphine Ligands. Acceleration Effects in Cross-Coupling of Bromophenols with Grignard Reagents (2007)
  • Author(s): Shunpei Ishikawa, Kei Manabe
  • Organizer: International Conference on Asymmetric Organocatalysis
  • Place of Presentation: Otsu
• [Presentation] 高性能触媒の創製を指向したオリゴアレーン型ホスフィン配位子の合成 (2007)
  • Author(s): 石川俊平, 眞鍋敬
  • Organizer: 日本化学会第87春季年会
  • Place of Presentation: 関西大学千里山キャンパス
• [Presentation] Ortho-Selective Cross Couping with Grignard Reagents in the Presence of Palladium Catalysts Bearing Hydroxylated Oligoarene-Type phosphines (2007)
  • Author(s): Manabe, K.
  • Organizer: 2007 Workshop on Organometallic Chemistry
  • Place of Presentation: 理研和光キャンパス
• [Presentation] Pd-Catalyzed Site-Selective Cross-Coupling of Dibromophenols with Grignard Reagents Using Oligoarene-Type Phosphine Ligands (2007)
  • Author(s): Ishikawa, S.
  • Organizer: 14th IUPAC International Symposium on Organo metallic Chemistry Directed Towards Organic Synthesis
  • Place of Presentation: 奈良
• [Presentation] Hydroxylated Oligoarene-Type Phosphine Ligands. Acceleration Effects in Cross-Coupling of Bromophenols with Grignard Reagents (2007)
  • Author(s): Ishikawa, S.
  • Organizer: International Conference on Asymmetric Organocatalysis
  • Place of Presentation: 大津
• [Presentation] Negishi Coupling Reactions of Zinciophenoxides and Their Application to Oligoarene Synthesis (2006)
  • Author(s): Haruka Shimizu, Kei Manabe
  • Organizer: 7th Tetrahedron Symposium
  • Place of Presentation: Kyoto
• [Presentation] Repetitive Two-Step Method for Multifunctionalized Oligoarene Synthesis through Rapid and Mild Cross-Coupling of Pinacol Esters of Hydroxyphenylboronic Acids (2006)
  • Author(s): Shunpei Ishikawa, Kei Manabe
  • Organizer: 7th Tetrahedron Symposium
  • Place of Presentation: Kyoto
• [Presentation] Zinciophenoxideを用いるオリゴアレーン類の二段階繰り返し合成法の開発研究 (2006)
  • Author(s): 清水春佳, 眞鍋敬
  • Organizer: 日本化学会第86春季年会
  • Place of Presentation: 日大理工船橋キャンパス
• [Presentation] ヒドロキシフェニルボロン酸類を用いる多置換オリゴアレーン類の効率的合成法の開発 (2006)
  • Author(s): 石川俊平, 眞鍋敬
  • Organizer: 日本化学会第86春季年会
  • Place of Presentation: 日大理工船橋キャンパス
• [Presentation] Repetitive Method for Oligoarene Synthesis (2005)
  • Author(s): Kei Manabe
  • Organizer: Stork Symposium on Organic Synthesis
  • Place of Presentation: Tokyo Institute of Technology
  • Year and Date: 2005-10-15
• [Presentation] オリゴアレーン類の新規二段階合成法の開発 (2005)
  • Author(s): 石川俊平, 眞鍋敬
  • Organizer: 第31回反応と合成の進歩シンポジウム
  • Place of Presentation: 神戸
• [Remarks]
  • URL: http://www.riken.jp/lab-www/manabeiru/Jindex.html
• [Remarks]
  • URL: http://www.riken.jp/lab-www/manabeiru/Jindex.html
• [Remarks]
  • URL: http://www.riken.jp/lab-www/manabeiru/Jindex.html
• [Patent(Industrial Property Rights)] カップリング用触媒およびそれに用いる配位子、ならびにクロスカップリング反応によるビアリール構造を有する化合物の製造方法 (2007)
  • Inventor(s): 眞鍋敬, 石川俊平
  • Industrial Property Rights Holder: 眞鍋敬, 石川俊平, 独立行政法人理化学研究所
  • Filing Date: 2007-07-24