Development of Regioselective Carbon-Carbon Bond Forming ReactionBetween Aromatic Compounds

• Project/Area Number: 17065002
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Tohoku University
• Principal Investigator: OI Shuichi Tohoku University, 環境保全センター, 教授 (00241547)
• Project Period (FY): 2005 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥17,500,000 (Direct Cost: ¥17,500,000); Fiscal Year 2008: ¥5,000,000 (Direct Cost: ¥5,000,000); Fiscal Year 2007: ¥5,000,000 (Direct Cost: ¥5,000,000); Fiscal Year 2006: ¥5,000,000 (Direct Cost: ¥5,000,000); Fiscal Year 2005: ¥2,500,000 (Direct Cost: ¥2,500,000)
• Keywords: 遷移金属錯体触媒 / 炭素-水素結合活性化 / 炭素-炭素結合形成 / クロスカップリング / ビアリ-ル合成 / 原子効率 / ルテニウム錯体 / C-H結合活性化 / ビアリール合成 / パラジウム錯体 / ホモカップリング / マルチプルへテロアリール化 / ヘテロアリール化 / アリル化 / アリルアセテート / 芳香族イミン / 芳香族オキサゾリン / ハロゲン化アリール

Research Abstract

本研究では,均一系遷移金属錯体触媒を用い,芳香族化合物の炭素-水素結合を直接芳香族炭素-炭素結合に変換する新しい合成反応の開発を行った.反応の位置選択性を制御する方法として,芳香環上の置換基の触媒金属への配位を利用することにより,その置換基のオルト位での選択的な炭素-炭素結合形成に成功した.以上の成果により,様々な2,2'-置換1,1'-ビアリ-ル化合物を効率的に合成することが可能となった.

Research Products

• [Journal Article] 配位を利用した芳香族C-H結合のオルト位選択的な直接アリール化反応 (2009)
  • Author(s): 大井秀一
  • Journal Title: 有機合成化学協会誌 67巻 Pages: 229-238
  • NAID: 10024968044
• [Journal Article] Ortho-Selective Arylation of Arylazoles with Aryl Bromides Catalyzed by Ruthenium Complexes (2008)
  • Author(s): Oi, S.; Sasamoto, H.; Funayama, R.; Inoue Y
  • Journal Title: Chem. Lett 37巻 Pages: 994-995
  • Peer Reviewed
• [Journal Article] Nitrogen-Directed Ortho-arylation and -Heteroarylation of Aromatic Rings Catalyzed by Ruthenium Complexes (2008)
  • Author(s): S. Oi, R. Funayama, T. Hattori, Y. Inoue
  • Journal Title: Tetrahedron 64巻 Pages: 6051-6059
  • Peer Reviewed
• [Journal Article] Nitrogen-Directed Ortho-Selective Homocoupling of Aromatic Compounds Catalyzed by Ruthenium Complexes (2008)
  • Author(s): S. Oi, H. Sato, S. Sugawara, Y. Inoue
  • Journal Title: Org. Lett 10巻 Pages: 1823-1826
  • Peer Reviewed
• [Journal Article] Direct C-H bond arylation of arenes with aryltin reagents catalysed by palladium complexes (2008)
  • Author(s): H. Kawai, Y. Kobayashi, S. Oi, Y. Inoue
  • Journal Title: Chem. Commun 巻数無 Pages: 1464-1466
  • Peer Reviewed
• [Journal Article] Nitrogen-Directed Ortho-Arylation and -Heteroarylation of Aromatic Rings Catalyzed by Ruthenium Complexes (2008)
  • Author(s): Shuichi Oi
  • Journal Title: Tetrahedron 64 Pages: 6051-6059
  • Peer Reviewed
• [Journal Article] Nitrogen-Directed Ortho-Selective Homocoupling of Aromatic Compounds Catalyzed by Ruthenium Complexes (2008)
  • Author(s): Shuichi Oi
  • Journal Title: Organic Letters 10 Pages: 1823-1826
  • Peer Reviewed
• [Journal Article] Ortho-Selective Arylation of Arylazoles with Aryl Bromides Catalyzed by Ruthenium Complexes (2008)
  • Author(s): Shuichi Oi
  • Journal Title: Chemistry Letters 37 Pages: 994-995
  • Peer Reviewed
• [Journal Article] Direct C-H bond arylation of arenes with aryltin reagents catalysed by palladium complexes (2008)
  • Author(s): Hiroshi Kawai
  • Journal Title: Chemical Communications Pages: 1464-1466
  • Peer Reviewed
• [Journal Article] Hydrogenation of Olefins Using Water and Zinc Metal Catalyzed by a Rhodium Complex (2006)
  • Author(s): T. Sato, S. Watanabe, H. Kiuchi, S. Oi, Y. Inoue
  • Journal Title: Tetrahedron Lett 47巻 Pages: 7703-7705
  • Peer Reviewed
• [Journal Article] Ortho-Selective Allylation of 2-Pyridylarenes with Allyl Acetates Catalyzed by Ruthenium Complexes (2006)
  • Author(s): S. Oi, Y. Tanaka, Y. Inoue
  • Journal Title: Organometallics 25巻 Pages: 4773-4778
  • Peer Reviewed
• [Journal Article] Asymmetric 1, 4-Addition of Aryltrialkoxysilanes toα, β-Unsaturated Esters and Amides Catalyzed by a Chiral Rhodium Complex, Tetrahedron (2006)
  • Author(s): S. Oi, A. Taira, Y. Honma, T. Sato, Y. Inoue
  • Journal Title: Asymmetry 17巻 Pages: 598-602
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Cycloisomerization of Allyl Propargyl Ethers: An Efficient Synthesis of 3, 4-Disubstituted Furans (2006)
  • Author(s): H. Kawai, S. Oi, Y. Inoue
  • Journal Title: Heterocycles 67巻 Pages: 101-105
  • Peer Reviewed
• [Journal Article] Ortho-Selective Allylation of 2-Pyridylarenes with Allyl Acetates Catalyzed by Ruthenium Complexes (2006)
  • Author(s): Shuichi Oi
  • Journal Title: Organometallics 25・20 Pages: 4773-4778
• [Journal Article] Asymmetric 1,4-Addition of Aryltrialkoxysilanes to α,β-Unsaturated Esters and Amids Catalyzed by a Chiral Rhodium Complex (2006)
  • Author(s): Shuichi Oi
  • Journal Title: Tetrahedron : Asymmetry 17・4 Pages: 598-602
• [Journal Article] Hydrogenation of Olefins Using Water and Zinc Metal Catalyzed by a Rhodium Complex (2006)
  • Author(s): Takashi Sato
  • Journal Title: Tetrahedron Letters 47・44 Pages: 7703-7705
• [Journal Article] Rhodium-Catalyzed Cycloisomerization of Allyl Propargyl Ethers : An Efficient Synthesis of 3,4-Disubstituted Furans (2006)
  • Author(s): Hiroshi Kawai
  • Journal Title: Heterocycles 67・1 Pages: 101-105
• [Journal Article] Palladium-Catalyzed Cyclocotrimerization of Propargyl Alcohols with Aryl Halides (2005)
  • Author(s): S. Oi, H. Orihara, H. Kawai, Y. Inoue
  • Journal Title: Heterocycles 66巻 Pages: 621-625
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Arylation of 2-Alkenylpyridines with Aryl Bromides: Alternative E, Z-Selectivity to Mizoroki-Heck Reaction (2005)
  • Author(s): S. Oi, K. Sakai, Y. Inoue
  • Journal Title: Org. Lett 7巻 Pages: 4009-4011
  • Peer Reviewed
• [Journal Article] Ortho-Selective Direct Cross-Coupling Reaction of 2-Aryloxazolines and 2-Arylimidazolines with Aryl and Alkenyl Halides Catalyzed by Ruthenium Complexes (2005)
  • Author(s): S. Oi, E. Aizawa, Y. Ogino, Y. Inoue
  • Journal Title: J. Org. Chem 70巻 Pages: 3113-3119
  • Peer Reviewed
• [Journal Article] Ortho-Selective Direct Cross-Coupling Reaction of 2-Aryloxazolines and 2-Arylimidazolines with Aryl and Alkenyl Halides Catalyzed by Ruthenium Complexes (2005)
  • Author(s): Shuichi Oi
  • Journal Title: The Journal of Organic Chemistry 70・8 Pages: 3113-3119
• [Journal Article] Ruthenium-Catalyzed Arylation of 2-Alkenylpyridines with Aryl Bromides : Alternative E, Z-Selectivity to Mizoroki-HecK Reaction (2005)
  • Author(s): Shuichi Oi
  • Journal Title: Organic Letters 7・18 Pages: 4009-4011
• [Journal Article] Palladium-Catalyzed Cyclocotrimerization of Propargyl Alcohols with Aryl Halides (2005)
  • Author(s): Shuichi Oi
  • Journal Title: Heterocycles 66・3 Pages: 621-625
• [Presentation] Nitrogen-Directed Ortho-Selective Homocoupling of Aromatic Compounds Catalyzed by Ruthenium Complexes (2008)
  • Author(s): Shuichi Oi
  • Organizer: Third International Conference on Advanced Organic Synthesis Directed toward the Ultimate Efficiency and Practicability
  • Place of Presentation: Ohtsu, Japan
  • Year and Date: 2008-05-27
• [Presentation] Nitrogen-Directed Regioselective Arylation of Aromatic C-H Bond Catalyzed by Ruthenium Complexes (2008)
  • Author(s): S. Oi
  • Organizer: 1st Japan-Singapore Bilateral Symposium on Catalysis
  • Place of Presentation: Singapore
  • Year and Date: 2008-01-07
• [Presentation] Nitrogen-Directed Regioselective Arylation of Aromatic C-H Bond Catalyzed by Ruthenium Complexes (2008)
  • Author(s): Shuichi Oi
  • Organizer: 1st Japan-Singapore Bilateral Symposium on Catalysis
  • Place of Presentation: National University of Singapore
  • Year and Date: 2008-01-07
• [Presentation] C-H結合を反応点とする芳香族カップリング反応 (2007)
  • Author(s): 大井秀一
  • Organizer: 近畿化学協会有機金属部会平成19年度第3回例会
  • Place of Presentation: 札幌
  • Year and Date: 2007-11-22
• [Presentation] Palladium-Catalyzed Direct C-H Phenylation: Cross-Coupling Reaction of Arenes with Phenyltintrichloride (2007)
  • Author(s): H. Kawai, Y. Kobayashi, S. Oi, Y. Inoue
  • Organizer: 14th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS-14)
  • Place of Presentation: Nara, Japan
  • Year and Date: 2007-08-04
• [Presentation] Transition Metal-Catalyzed Construction of Substituted Furans and Dihydrofurans (2007)
  • Author(s): H. Kawai, S. Oi, Y. Inoue
  • Organizer: Second International Conference on Advanced Organic Synthesis Directed toward the Ultimate Efficiency and Practicability
  • Place of Presentation: Ohtsu, Japan
  • Year and Date: 2007-05-29
• [Presentation] 窒素原子による配位を利用したC-H結合活性化 (2007)
  • Author(s): 大井秀一
  • Organizer: 日本化学会第87春期年会
  • Place of Presentation: 大阪
  • Year and Date: 2007-03-27
• [Presentation] Transition Metal-Catalyzed Construction of Substituted Furans and Dihydrofurans (2006)
  • Author(s): H. Kawai, H. Orihara, S. Oi, Y. Inoue
  • Organizer: The Tenth International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-10)
  • Place of Presentation: Kyoto, Japan
  • Year and Date: 2006-11-15
• [Presentation] 芳香族C-H結合を反応点とする直接カップリング反応の開拓 (2006)
  • Author(s): 大井秀一
  • Organizer: 平成18年度化学系学協会東北大会
  • Place of Presentation: 秋田
  • Year and Date: 2006-09-23
• [Presentation] Asymmetric 1, 4-Addition of Alkenylzirconium Reagents toα, β-Unsaturated Ketones Catalyzed by Chiral Rhodium Complexes (2005)
  • Author(s): T. Sato, S. Oi, Y. Inoue
  • Organizer: Pacifichem 2005
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2005-12-18
• [Presentation] Asymmetric 1, 4-Addition of Organosiloxanes toα, β-Unsaturated Carbonyl Compounds Catalyzed by a Chiral Rhodium Complex (2005)
  • Author(s): S. Oi, A. Taira, Y. Honma, Y. Inoue
  • Organizer: Pacifichem 2005
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2005-12-18
• [Presentation] Ruthenium-Catalyzed Arylation of 2-Alkenylpyridines with Aryl Bromides: Alternative E, Z-Selectivity to Mizoroki-Heck Reaction (2005)
  • Author(s): K. Sakai, S. Oi, Y. Inoue
  • Organizer: Pacifichem 2005
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2005-12-18
• [Presentation] Ortho Selective Direct Cross-Coupling Reaction of 2-Aryloxazolines and 2-Arylimidazolines with Aryl and Alkenyl Halides Catalyzed by Ruthenium Complexes (2005)
  • Author(s): S. Oi, E. Aizawa, Y. Ogino, Y. Inoue
  • Organizer: Pacifichem 2005
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2005-12-17
• [Presentation] Nitrogen-Directed Regioselective Arylation of Aromatic C-H Bond Catalyzed by Ruthenium Complexes (2005)
  • Author(s): S. Oi
  • Organizer: 5th Tateshina Conference on Organic Chemistry
  • Place of Presentation: Nagano, Japan
  • Year and Date: 2005-11-12
• [Presentation] Nitrogen-Directed Regioselective Arylation of Aromatic C-H Bond Catalyzed by Ruthenium Complexes (2005)
  • Author(s): S. Oi
  • Organizer: 4th Asian-European Symposium
  • Place of Presentation: Nagasaki, Japan
  • Year and Date: 2005-11-07
• [Book] 有機委合成反応実践ガイド (2010)
  • Author(s): 大井秀一
  • Publisher: 化学同人
• [Patent(Industrial Property Rights)] 多置換芳香族化合物の製造方法及び多置換芳香族化合物 (2007)
  • Inventor(s): 大井秀一, 井上祥雄, 北弘志, 押山智寛
  • Industrial Property Rights Holder: コニカミノルタホールディングス株式会社, 国立大学法人東北大学
  • Patent Publication Number: 2008-222687
  • Filing Date: 2007-03-16
• [Patent(Industrial Property Rights)] ビアリ-ル化合物の製造方法 (2007)
  • Inventor(s): 井上祥雄, 大井秀一
  • Industrial Property Rights Holder: 長瀬産業株式会社, 国立大学法人東北大学
  • Patent Publication Number: 2008-169125
  • Filing Date: 2007-01-09
• [Patent(Industrial Property Rights)] ビアリール化合物の製造方法 (2007)
  • Inventor(s): 井上祥雄, 大井秀一
  • Industrial Property Rights Holder: 長瀬産業株式会社, 東北大学
  • Industrial Property Number: 2007-001562
  • Filing Date: 2007-01-09