Innovative Advanced Protocols for Constructing Carbon-Carbon Bonds via Activation of Aromatic Carbon-Hydrogen Bond

• Project/Area Number: 17065016
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Keio University
• Principal Investigator: KAKIUCHI Fumitoshi Keio University, 理工学部, 教授 (70252591)
• Project Period (FY): 2005 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥18,900,000 (Direct Cost: ¥18,900,000); Fiscal Year 2008: ¥5,400,000 (Direct Cost: ¥5,400,000); Fiscal Year 2007: ¥5,400,000 (Direct Cost: ¥5,400,000); Fiscal Year 2006: ¥5,400,000 (Direct Cost: ¥5,400,000); Fiscal Year 2005: ¥2,700,000 (Direct Cost: ¥2,700,000)
• Keywords: ルテニウム錯体触媒 / 芳香族化合物 / 芳香族炭素-水素結合切断 / 炭素-炭素結合生成 / 酸クロライド類 / 不活性結合切断 / ヘテロ芳香族化合物 / 有機ホウ素化号物 / 炭素-酸素結合切断 / アルケニルエステル / 有機ホウ素化合物 / 炭素-水素結合切断 / 炭素-ヘテロ原子結合切断 / 還移金属錯体 / 触媒反応

Research Abstract

Innovative Advanced Protocols 本研究では,遷移金属触媒を用いた芳香族炭素-水素結合切断を経る炭素-炭素結合生成を伴う反応の機構の解明と新規カップルリング反応の開発を行った。その結果、アルケニルエステルを用いたアルケニル化反応、アリール典型金属化合物とのカップリング反応、エステル基やアミド基等の極性官能基の導入反応、アセンキノン類を多置換アセン類へ短工程で変換する新手法など、既存の方法では合成が困難であった化合物を簡便に合成できる手法の開発に成功した。

Research Products

• [Journal Article] Cleavage of C-N Bonds in Aniline Derivatives on a Ruthenium Center and Its Relevance to Catalytic C-C Bond Formation (2009)
  • Author(s): Tetsuro Koreeda, Takuya Kochi, and Fumitoshi Kakiuchi
  • Journal Title: J. Am. Chem. Soc., 131 Pages: 7238-7239
  • Peer Reviewed
• [Journal Article] Convenient Synthesis of Tetra- and Hexaarylanthracenes by Means of RuH2(CO)(PPh3)3-Catalyzed C-H Arylation of Anthraquinone with Arylboronates; (2009)
  • Author(s): Kentaroh Kitazawa, Takuya Kochi, Mitsuo Sato, and Fumitoshi Kakiuchi
  • Journal Title: Org. Lett 11(9) Pages: 951-954
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Amino-and Alkoxycarbonylations with Carbamoyl Chlorides and Alkyl Chloroformates via Aromatic C-H Bond Cleavage; (2009)
  • Author(s): Takuya Kochi, Seiya Urano, Hajime Seki, Eiichiro Mizushima, Mitsuo Sato, and Fumitoshi, Kakiuchi
  • Journal Title: J. Am. Chem. Soc. 131(8) Pages: 2792-2793
  • Peer Reviewed
• [Journal Article] Unique Effect of Coordination of an Alkene Moiety in Products on Ruthenium-Catalyzed Chemoselective C-H Alkenylation; (2009)
  • Author(s): Satoshi Ueno, Takuya Kochi, Naoto Chatani, and Fumitoshi Kakiuchi
  • Journal Title: Org. Lett., 11(4) Pages: 855-858
  • Peer Reviewed
• [Journal Article] Convenient Synthesis of Tetra-and Hexaarylanthracenes by Means of RuH2(CO)(PPh3)3-Catalyzed C-H Arylation of Anthraquinone with Arylboronates (2009)
  • Author(s): Kentaroh Kitazawa, Takuya Kochi, and Fumitoshi Kakiuchi
  • Journal Title: Org. Lett 11(掲載確定)
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Amino-and Alkoxycarbonylations with Carbamoyl Chlorides and Alkyl Chloroformates via Aromatic C-H Bond Cleavage (2009)
  • Author(s): Takuya Kochi, SeiyaUrano, Hajime, Seki, Eiichiro Mizushima, Mitsuo Sato, and Fumitoshi Kakiuchi
  • Journal Title: J. Am. Chem. Soc 131 Pages: 2792-2793
  • Peer Reviewed
• [Journal Article] Unique Effect of Coordination of an Alkene Moiety in Products on Ruthenium-Catalyzed Chemoselective C-H Alkenylation (2009)
  • Author(s): Satoshi Ueno, Takuya Kochi, Naoto Chatani, and Fumitoshi Kakiuchi
  • Journal Title: Org. Lett 11 Pages: 855-858
  • Peer Reviewed
• [Journal Article] Transition Metal-Catalyzed Carbon-Carbon Bond Formation via Carbon-Hydrogen Bond Cleavage (2008)
  • Author(s): Fumitoshi Kakiuchi and Takuya Kochi
  • Journal Title: Synthesis (10) Pages: 3013-3039
  • Peer Reviewed
• [Journal Article] The Ru(cod)(cot)-Catalyzed Alkenylation of Aromatic C-H Bonds with Alkenyl Acetates; (2007)
  • Author(s): Yusuke Matsuura, Masaru Tamura, Takuya Kochi, Mitsuo Sato, Naoto Chatani, and Fumitoshi Kakiuchi,
  • Journal Title: J. Am. Chem. Soc., 129(32) Pages: 9858-9859
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Carbon-Carbon Bond Formation via the Cleavage of an Unreactive Aryl Carbon-Nitrogen Bond in Aniline Derivatives with Organoboronates (2007)
  • Author(s): Satoshi Ueno, Naoto Chatani, and Fumitoshi Kakiuchi
  • Journal Title: J. Am. Chem. Soc., 129(19) Pages: 6098-6099
  • Peer Reviewed
• [Journal Article] Regioselective Alkenylation of Aromatic Ketones with Alkenylboronates Using a RuH2(CO)(PPh3)3-Catalyst via Carbon-Hydrogen Bond Cleavage Regioselective (2007)
  • Author(s): Satoshi Ueno, Naoto Chatani, and Fumitoshi Kakiuchi
  • Journal Title: J. Org. Chem 72(9) Pages: 3600-3602
  • Peer Reviewed
• [Journal Article] Ru/C-Catalyzed Carbonylation at ortho-C-H Bonds in 2-Phenylpyridines (2007)
  • Author(s): Shinya Imoto, Takeshi Uemura, Fumitoshi Kakiuchi, and; Naoto Chatani
  • Journal Title: Synlett Pages: 170-172
  • Peer Reviewed
• [Journal Article] The Ru(cod)(cot)-Catalyzed Alkenylation of Aromatic C-H Bonds with Alkenyl Acetates (2007)
  • Author(s): Yusuke Matsuura, Masaru Tamura, Takuya Kochi, Mitsuo Sato, Naoto Chatani, and Fumitoshi Kakiuch
  • Journal Title: J. Am. Chem.Soc. 129巻・32号 Pages: 9858-9859
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Carbon-Carbon Bond Formation via the Cleavage ofan Unreactive Aryl Carbon-Nitrogen Bond m Aniline Derivatives withOrganoboronates (2007)
  • Author(s): Satoshi Ueno, Naoto Chatani, and Fumitoshi Kakiuchi
  • Journal Title: J. Am. Chem.Soc. 129巻・19号 Pages: 6098-6099
  • Peer Reviewed
• [Journal Article] Regioselective Alkenylation of Aromatic Ketones with Alkenylboronates Using a RuH_2(CO)(PPh_3)_3-Catalyst via Carbon-Hydrogen Bond Cleavage (2007)
  • Author(s): Satoshi Ueno, Naoto Chatani, Fumitoshi Kakiuchi
  • Journal Title: Journal of Organic Chemistry 72巻(印刷中)
• [Journal Article] Ru/C-Catalyzed Carbonylation at ortho-C-H Bonds in 2-Phenylpyridines (2007)
  • Author(s): Shinya Imoto, Takeshi Uemura, Fumitoshi Kakiuchi, Naoto Chatani
  • Journal Title: Synlett 1号 Pages: 170-172
• [Journal Article] Direct Observation of the Oxidative Addition of the Aryl Carbon-Oxygen Bond to a Ruthenium Complex and Consideration of the Relative Reactivity between Aryl Carbon-Oxygen and Aryl Carbon-Hydrogen Bonds (2006)
  • Author(s): Satoshi Ueno, Eiichiro Mizushima, Naoto Chatani, and Fumitoshi Kakiuchi
  • Journal Title: J. Am. Chem. Soc., 128(51) Pages: 16516-16517
  • Peer Reviewed
• [Journal Article] Synthesis of [Ru(CO)2 (PPh3)(SP)] and Ru(CO)(PPh3)2(SP)] and Their CatalyticActivities for the Hydroamination of Phenylacetylene (2006)
  • Author(s): Eiichiro Mizushima, Naoto Chatani, and Fumitoshi Kakiuchi,
  • Journal Title: J. Organomet. Chem., 691(26) Pages: 5739-5745
  • Peer Reviewed
• [Journal Article] Observation of the Oxidative Addition of the Aryl Carbon-Oxygen Bond to a Ruthenium Complex and Consideration of the Relative Reactivity between Aryl Carbon-Oxygen and Aryl Carbon-Hydrogen Bonds (2006)
  • Author(s): Satoshi Ueno, Eiichiro Mizushima, Naoto Chatani, Fumitoshi Kakiuchi
  • Journal Title: Journal of the American Chemical Society 128巻51号 Pages: 16516-16517
• [Presentation] 炭素-水素結合を利用した炭素官能基導入の新手法 (2009)
  • Author(s): 垣内史敏
  • Organizer: 第57回有機合成化学協会関東支部シンポジウム
  • Place of Presentation: 早稲田大学、東京
  • Year and Date: 2009-05-09
• [Presentation] ルテニウムホスフィン錯体の2'-アミノビバロフェノンとの反応性に関する研究 (2009)
  • Author(s): 是枝徹郎、河内卓彌、垣内史敏
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学
  • Year and Date: 2009-03-28
• [Presentation] ルテニウム触媒による炭素-水素結合の位置選択的官能基化を利用した多置換ポリアセン類の効率的合成 (2009)
  • Author(s): 北澤謙太郎、松村大植、河内卓彌、垣内史敏
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学
  • Year and Date: 2009-03-27
• [Presentation] ルテニウム触媒による芳香族炭素-水素結合切断を経る位置選択的アルケニル化反応におけるアルケニルエステルの反応機構に与える影響 (2009)
  • Author(s): 田村賢、河内卓彌、垣内史敏
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学
  • Year and Date: 2009-03-27
• [Presentation] RuCl2(PPh3)3-Catalyzed Chelation-Assisted Alkoxy-and Aminocarbonylation of Aromatic C-H Bond (2008)
  • Author(s): 垣内史敏
  • Organizer: The 9th International Symposium on Organic Reactions
  • Place of Presentation: Nice Plaza Hotel, Taiwan
  • Year and Date: 2008-11-22
• [Presentation] RuC1_2(PPh_3)_3-Catalyzed Chelation-Assisted Alkoxy-and Aminocarbonvlation of Aromatic C-H Bond Bonds (2008)
  • Author(s): 垣内史敏
  • Organizer: The 9th International Symposium on Organic Reactions
  • Place of Presentation: Nice Plaza Hotel, 台湾
  • Year and Date: 2008-11-22
• [Presentation] Ruthenium-Catalyzed Cross-Coupling Reactions of Aromatic Ketones with Organoboronates via Aryl Carbon-Oxygen and-Nitrogen Bonds Cleavage (2008)
  • Author(s): 垣内史敏
  • Organizer: The 9th International Symposium on Organic Reactions Pre-Symposium
  • Place of Presentation: National Taiwan Normal University, Taiwan
  • Year and Date: 2008-11-19
• [Presentation] 芳香族炭素-水素結合切断を経るアルケニル化の新手法 (2008)
  • Author(s): 垣内史敏
  • Organizer: The 9th International Symposium on Organic Reactions Pre-Symposium
  • Place of Presentation: National Taiwan Normal University、台湾
  • Year and Date: 2008-11-19
• [Presentation] 炭素-水素結合切断を機軸とするπ共役芳香族化合物の新規合成法の開発 (2008)
  • Author(s): 垣内史敏
  • Organizer: 分子触媒セミナー
  • Place of Presentation: 東京農工大学
  • Year and Date: 2008-11-15
• [Presentation] A New Strategy for Synthesis of π-Conjugated Aromatic Compounds via C-H Bond Cleavage (2008)
  • Author(s): 垣内史敏
  • Organizer: Japan-Korea Joint Symposium on Functional Materials toward Future Catalysts: Chemistry Showcase
  • Place of Presentation: Korea Advanced Institute Scienceand Technology, Korea
  • Year and Date: 2008-11-04
• [Presentation] A New Strategy for Synthesis of n-Conjugated Aromatic Compounds via C-H Bond Cleavaae (2008)
  • Author(s): 垣内史敏
  • Organizer: Japan-Korea Joint Symposium on Functional Materials toward Future Catalysts : Chemistry Showcase
  • Place of Presentation: Korea Advanced Institute Science and Technology、韓国
  • Year and Date: 2008-11-04
• [Presentation] 芳香族炭素-水素結合切断を利用した官能基導入の新手法 (2008)
  • Author(s): 垣内史敏
  • Organizer: 機能材料設計学セミナー
  • Place of Presentation: 京都大学
  • Year and Date: 2008-10-14
• [Presentation] ルテニウム錯体による位置選択的炭素-水素結合切断を経る芳香族化合物と酢酸アルケニルとのカップリング反応 (2008)
  • Author(s): 垣内史敏、田村賢、河内卓彌
  • Organizer: 第55回有機金属討論会
  • Place of Presentation: 大阪府立大学
  • Year and Date: 2008-09-30
• [Presentation] ルテニウム触媒による芳香族炭素-水素結合切断を利用した位置選択的アルコキシカルボニル化およびアミノカルボニル化反応 (2008)
  • Author(s): 浦野誠也、関一、水島英一郎、河内卓彌、佐藤光央、垣内史敏
  • Organizer: 第55回有機金属討論会
  • Place of Presentation: 大阪府立大学
  • Year and Date: 2008-09-30
• [Presentation] ルテニウム錯体による2'-アミノフェニルケトン類の芳香族炭素-窒素結合切断の観測 (2008)
  • Author(s): 是枝徹郎、河内卓彌、垣内史敏
  • Organizer: 第55回有機金属討論会
  • Place of Presentation: 大阪府立大学
  • Year and Date: 2008-09-29
• [Presentation] 芳香族炭素-水素結合切断を経るアルケニル化の新手法 (2008)
  • Author(s): 垣内史敏
  • Organizer: 平成20年度若手研究者のためのセミナー
  • Place of Presentation: 名古屋大学
  • Year and Date: 2008-07-25
• [Presentation] Ruthenium-Catalyzed Alkenylation of Aromatic C-H Bonds with Alkenyl Acetates (2008)
  • Author(s): 垣内史敏、田村賢、河内卓彌
  • Organizer: 23rd International Conference on Organometallic Chemistry
  • Place of Presentation: Rennes 1 University, France
  • Year and Date: 2008-07-15
• [Presentation] Ruthenium-Catalyzed Alkenylation of Aromatic C-H Bonds with Alkenvl Acetates (2008)
  • Author(s): 垣内史敏、田村賢、河内卓彌
  • Organizer: 23rd International Conference on Organometallic Chemistry
  • Place of Presentation: Rennes 1 University、フランス
  • Year and Date: 2008-07-15
• [Presentation] Ruthenium-Catalyzed Coupling Reaction of Aromatic Ketones with Compounds (2005)
  • Author(s): 垣内史敏
  • Organizer: PACIFICHEM2005 (2005 環太平洋国際化学会議)
  • Place of Presentation: Waikiki, Hawaii
  • Year and Date: 2005-12-17
• [Presentation] Ruthenium-Catalyzed Coupling of Aromatic Compounds with Organoboronates via Carbon-Hydrogen Bond Cleavage (2005)
  • Author(s): 垣内史敏
  • Organizer: Pre OMCOS 13
  • Place of Presentation: Paris, France
  • Year and Date: 2005-07-15
• [Book] Topics in Organometallic Chemistry: Directed Metallation: "Catalytic Addition of C-H Bonds to C-C Multiple Bonds" (2007)
  • Author(s): Fumitoshi Kakiuchi
  • Publisher: Springer: Berlin
• [Patent(Industrial Property Rights)] 芳香族化合物及びその製造方法 (2009)
  • Inventor(s): 垣内史敏、寺井宏樹
  • Industrial Property Rights Holder: 学校法人慶應義塾、住友化学株式会社
  • Industrial Property Number: 2009-109577
  • Filing Date: 2009-04-28
• [Patent(Industrial Property Rights)] 電気分解を利用した芳香族ハロゲン化合物の製造方法 (2009)
  • Inventor(s): 垣内史敏
  • Industrial Property Rights Holder: 学校法人慶應義塾
  • Industrial Property Number: 2009-056402
  • Filing Date: 2009-03-10
• [Patent(Industrial Property Rights)] 芳香族化合物の製造方法 (2009)
  • Inventor(s): 垣内史敏、寺井宏樹
  • Industrial Property Rights Holder: 学校法人慶應義塾、住友化学株式会社
  • Industrial Property Number: 2009-021271
  • Filing Date: 2009-02-02
• [Patent(Industrial Property Rights)] 芳香族カルボニル化合物の製造方法 (2009)
  • Inventor(s): 垣内史敏、小熊潤
  • Industrial Property Rights Holder: 学校法人慶應義塾、住友化学株式会社
  • Filing Date: 2009-01-25
  • Overseas
• [Patent(Industrial Property Rights)] 三置換芳香族化合物 (2009)
  • Inventor(s): 垣内史敏、寺井宏樹
  • Industrial Property Rights Holder: 学校法人慶應義塾、住友化学株式会社
  • Industrial Property Number: 2008-014915
  • Filing Date: 2009-02-02
  • Overseas