Exploitation of aerobic catalytic oxidation reaction under mild conditions

• Project/Area Number: 19550115
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Okayama University of Science
• Principal Investigator: MURAHASHI Shun-Ichi Okayama University of Science, 客員教授(常勤扱) (60029436)
• Project Period (FY): 2007 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000); Fiscal Year 2009: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2008: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2007: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
• Keywords: 酸素酸化反応 / C-H結合活性化 / ルテニウム触媒 / Biomimetic反応 / アミンの酸化 / シアノアミンの合成 / アミノ酸合成 / 不活性炭化水素の酸化 / 酸素酸化触媒反応 / アミンノ酸化 / オキシムの合成 / 選択的合成 / シアノ化反応 / αアミノニトリル / フラビン触媒

Research Abstract

Ruthenium-catalyzed oxidative cyanation of tertiary amines with molecular oxygen in the presence of sodium cyanide and acetic acid gives the corresponding α-aminonitriles, which are highly useful intermediates for organic synthesis. The reaction is the first demonstration of direct sp^3C-H bond activation α to nitrogen followed by carbon-carbon bond formation under aerobic oxidation conditions.

Research Products

• [Journal Article] Synthesis of 2-substituted quinones, vitamin K3, and vitamin K1 from p-cresol. BF3・OEt2-catalyzed methyl migration of 4-tert-butyldioxycyclohexadienones (2010)
  • Author(s): Shun-Ichi Murahashi, Akiko Fujii, Yasutaka Inubushi, Naruyoshi Komiya
  • Journal Title: Tetrahedron Lett. Pages: 2339-2341
  • Peer Reviewed
• [Journal Article] Synthesis of 2-substituted quinones, vitamin K_3, and vitamin K_1 from p-cresol. BF_3・OEt_2-catalyzed methyl migration of 4-tert-butyldioxycyclohexadienones (2010)
  • Author(s): Shun-Ichi Murahashi
  • Journal Title: Tetrahedron Letters Volume: 51 Pages: 2339-2341
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Regioselective Reactions of Nitriles and 1,3-Dicarbonyl Compounds with Terminal Alkynes (2009)
  • Author(s): Shun-Ichi Murahashi, Takeshi Naota, Yoshinori Nakano
  • Journal Title: Synlett Pages: 3355-3359
  • Peer Reviewed
• [Journal Article] Rhenium-Catalyzed Addition of Carbonyl Compounds to the Carbon-Nitrogen Triple Bonds of Nitriles : α-C-H Activation of Carbonyl Compounds (2009)
  • Author(s): Hikaru Takaya, Masatsugu Ito, Shun-Ichi Murahashi
  • Journal Title: J.Am.Chem.Soc. 131 Pages: 10824-10825
  • Peer Reviewed
• [Journal Article] Iridium-Catalyzed Reactions of Trifluoromethylated Compounds with Alkenes : A Csp^3---H Bond Activation α to the Trifluoromethyl Group (2009)
  • Author(s): Yong Guo, Xiaoming Zhao, Dazhi Zhang, Shun-Ichi Murahashi
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 2047-2049
  • Peer Reviewed
• [Journal Article] Rhenium-catalyzed Addition of Carbonyl Compounds to the Carbon-Nitrogen Triple Bonds of Nitriles (2009)
  • Author(s): Hikaru Takaya
  • Journal Title: Journal of the American Chemical Society Volume: 131 Pages: 10824-10825
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Regioselective Reactions of Nitriles and 1,3-Dicarbonyl Compounds with Terminal Alkynes (2009)
  • Author(s): Shun-Ichi Murahashi
  • Journal Title: Synlett Pages: 3355-3359
  • Peer Reviewed
• [Journal Article] Iridium-Catalyzed Reactions of Trifluoromethylated Compounds with Alkenes : A Csp3-H bond Activation α to the Trifluoromethyl Group (2009)
  • Author(s): Yong Guo
  • Journal Title: Angewandte Chemie International Edition Volume: 48 Pages: 2047-2049
  • Peer Reviewed
• [Journal Article] Iridium-Catalyzed Reactions of Trifluoromethylated Compounds with Alkenes : A Csp3-H bond Activation ato the Trifluoromethyl Group (2009)
  • Author(s): Yong Guo
  • Journal Title: Angew. Chem. Int. Ed. 48 Pages: 2047-2049
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Oxidative Cyanation of Tertiary Amines with Molecular Oxygen or Hydrogen Peroxide and Sodium Cyanide : sp^3 C-H Bond Activation and Carbon-Carbon Bond Formation (2008)
  • Author(s): Shun-Ichi Murahashi, Takahiro Nakae, Hiroyuki Terai, Naruyoshi Komiya
  • Journal Title: J.Am.Chem.Soc. 130 Pages: 11005-11012
  • Peer Reviewed
• [Journal Article] Shun-Ichi Murahashi, Hikaru Takaya, Switchable C- and N-Bond Isomers of Transition-Metal Cyanocarbanions : Synthesis and Interconversions of Cyclopentadienyl Ruthenium Complexes of Phenylsulfonylacetonitrile Anions (2008)
  • Author(s): Takeshi Naota, Akio Tanna, Shigeaki Kamuro, Masayuki Hieda, Kazuki Ogata
  • Journal Title: Chem.Eur.J. 14 Pages: 2482-2498
  • Peer Reviewed
• [Journal Article] Ruthenium Catalyzed Biomimetic Oxidation in Organic Synthesis Inspired by Cytochrome P-450 (2008)
  • Author(s): Shun-Ichi Murahashi, Dazhi Zhang
  • Journal Title: Chemical Society Reviews 37 Pages: 1490-1501
  • Peer Reviewed
• [Journal Article] Aerobic Oxidation of Primary Amines to Oximes Catalyzed by DPPH and WO_3/Al_2O_3 (2008)
  • Author(s): Ken Suzuki, Tomonari Watanabe, Shun-Ichi Murahashi
  • Journal Title: Angew.Chem.Int.Ed. 47 Pages: 2079-2081
  • Peer Reviewed
• [Journal Article] Aerobic Oxidative Transformation of Primary Amines to Oximes Catalyzed by 1, 1-Dipheny1-2-picrylhydrazyl (DPPH) and Tungstated Alumina (2008)
  • Author(s): Ken Suzuki
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 2079-2081
  • Peer Reviewed
• [Journal Article] Ruthenium Catalyzed Biomimetic Oxidation in Organic Synthesis Inspired by Cytochrome P-450 (2008)
  • Author(s): Shun-Ichi Murahashi
  • Journal Title: Chemical Society Reviews 37 Pages: 1490-1501
  • Peer Reviewed
• [Journal Article] Switchable C-and N-Bond Isomers of Transition-Metal Cyanocarvbanions : Synthesis and Interconversions of Cyclopentadienyl Ruthenium Complexes of Phenylsulfonylacetonitrile Anions (2008)
  • Author(s): Takeshi Naota
  • Journal Title: Chem. Eur. J. 14 Pages: 2482-2498
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Oxidative Cyanation of Tertiary Amines with Molecular Oxygen or Hydrogen Peroxide and Sodium Cyanide : sp3 C-H Bond Activation and Carbon-Carbon Bond Formation (2008)
  • Author(s): Shun-Ichi Murahashi
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 11005-11012
  • Peer Reviewed
• [Journal Article] Aerobic Ruthenium-Catalyzed Oxidative Transformation of Secondary Amines to Imines (2007)
  • Author(s): Shun-Ichi Murahashi, Yuriko Okano, Hideomi Sato, Takahiro Nakae, Naruyoshi Komiya
  • Journal Title: Synlett Pages: 1675-1678
  • Peer Reviewed
• [Journal Article] Aerobic Ruthenium-Catalyzed Oxidative Transformation of Secondary Amines to Imines (2007)
  • Author(s): S.-I. Murahashi, Y. Okano, H. Sato, T. Nakae, N. Komiya
  • Journal Title: Synlett. 11 Pages: 1675-1678
  • Peer Reviewed
• [Journal Article] Oxidation of Olefins Catalyzed by New Naphthyl-ruthenium(III)Complexes (2007)
  • Author(s): L. Provins, S-I. Murahashi
  • Journal Title: Arkivoc X Pages: 107-120
  • Peer Reviewed
• [Journal Article] Development of Ruthenium Catalyzed Oxidation Reaction Inspired by Cytochrome P-450 (2007)
  • Author(s): S.-I. Murahashi
  • Journal Title: J.Synth.Org.Chem.Jpn. 65 Pages: 2-13
  • NAID: 10018461586
  • Peer Reviewed
• [Presentation] Transition-metal catalyzed reactions of carbonyl compounds and trifluoromethylated compounds : A sp^3C-H bond activation induced by α heteroatom effect (2010)
  • Author(s): 村橋俊一
  • Organizer: The International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Hawaii, USA
  • Year and Date: 2010-12-18
• [Presentation] Transition-metal catalyzed reactions of carbonyl compounds and trofuloromethylated compounds : A sp^3C-H bond activation induced by a heteroatom effect (2010)
  • Author(s): Shun-Ichi Murahashi
  • Organizer: The International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Hawaii, USA
  • Year and Date: 2010-12-18
• [Presentation] Exploitation of Green Catalytic Reactions for Sustainable Development (2010)
  • Author(s): 村橋俊一
  • Organizer: Takasago Symposium 2010-New Paradigm Led by Catalysts-
  • Place of Presentation: Tokyo Japan
  • Year and Date: 2010-12-03
• [Presentation] Exploitation of Green Catalytic Reactions for Sustainable Development (2010)
  • Author(s): Shun-Ichi Murahashi
  • Organizer: Takasago Symposium 2010-New Paradigm Led by Catalysts-
  • Place of Presentation: Tokyo, Japan
  • Year and Date: 2010-12-03
• [Presentation] 有機合成化学の展望-持続可能な発展に向けて- (2010)
  • Author(s): 村橋俊一
  • Organizer: 日本化学連合・有機合成化学会合同公開講演会-持続可能な社会に向けての有機合成化学の役割-
  • Place of Presentation: 東京工業大学
  • Year and Date: 2010-11-27
• [Presentation] 有機合成化学の展望-持続可能な発展に向けて- (2010)
  • Author(s): 村橋俊一
  • Organizer: 日本化学連合・有機合成化学会合同公開講演会
  • Place of Presentation: 東京工業大学
  • Year and Date: 2010-11-27
• [Presentation] 有機合成触媒反応-新しい原理・手法を求めて- (2010)
  • Author(s): 村橋俊一
  • Organizer: 有機合成化学特別講演会 第190回懇談会
  • Place of Presentation: 東京大学
  • Year and Date: 2010-09-11
• [Presentation] Green Catalytic Reactions for Sustainable Development (2009)
  • Author(s): Shun-Ichi Murahashi
  • Organizer: International Conference on Green and Sustainable Chemistry
  • Place of Presentation: Furama Riverfront, Singapore
  • Year and Date: 2009-08-03
• [Presentation] Green Catalytic Reactions for Sustainable Development (2009)
  • Author(s): 村橋俊一
  • Organizer: International Conference on Green & Sustainable Chemistry
  • Place of Presentation: Singapore
• [Presentation] Green Catalytic Reactions for Sustainable Development (2008)
  • Author(s): Shun-Ichi Murahashi
  • Organizer: 11^<th> International Symposium on Natural Products Chemistry
  • Place of Presentation: Karachi, Pakistan
  • Year and Date: 2008-10-30
• [Presentation] Recent Advances in Green Catalytic Reactions with Transition-Metal Catalysts (2008)
  • Author(s): Shun-Ichi Murahashi
  • Organizer: 15^<th> National Conference on Organometallic Chemistry
  • Place of Presentation: Nanjing, China
  • Year and Date: 2008-10-21
• [Presentation] Green Catalytic Reactions for Sustainable Development (2008)
  • Author(s): Shun-Ichi Murahashi
  • Organizer: 9^<th> International Symposium on Green Chemistry
  • Place of Presentation: Hefei, China
  • Year and Date: 2008-05-12
• [Presentation] Green Catalytic Reactions for Sustainable Development (2008)
  • Author(s): 村橋俊一
  • Organizer: 11th International Symposium on Natural Products Chemistry
  • Place of Presentation: Karachi, Pakistan
• [Presentation] Recent Advances in Green Catalytic Reactions with Transition-metal Catalysts (2008)
  • Author(s): 村橋俊一
  • Organizer: 15th National Conference on Organometallic Chemistry
  • Place of Presentation: Nanjing, China
• [Presentation] Green Catalytic Reactions for Sustainable Development (2008)
  • Author(s): 村橋俊一
  • Organizer: 9th International Symposium on Green Chemistry in China
  • Place of Presentation: Hefei, China
• [Presentation] Green Catalytic Reactions for Sustainable Development (2007)
  • Author(s): 村橋俊一
  • Organizer: Farewell Symposium Roger Sheldon A Journey in Green Chemistry
  • Place of Presentation: Delft, The Netherlands
• [Presentation] Biomimetic Catalytic Oxidation Reactions for Organic Synthesis-A Way for Green Chemistry (2007)
  • Author(s): 村橋俊一
  • Organizer: A STAR-Noyori Forum Joint Symposium
  • Place of Presentation: Singapore
• [Book] 2010ノーベル化学賞受賞記念特集:クロスカップリング反応の軌跡(パラジウム触媒を用いる有機ハロゲン化物と有機リチウム化合物、ヘテロ原子求核剤のクロスカップリング反応 Vol.64) (2011)
  • Author(s): 村橋俊一
  • Publisher: 化学と工業
• [Book] 化学で何ができるか 未来につながる「化学」の架け橋(有機合成協会編)(グリーンケミストリー) (2011)
  • Author(s): 村橋俊一
  • Publisher: 化学工業日報社
• [Book] 最新グリーンケミストリー、持続可能社会のための化学(御園生誠、村橋俊一編)(グリーン触媒-均一系錯体触媒) (2011)
  • Author(s): 村橋俊一
  • Publisher: 講談社
• [Book] 最新グリーンケミストリー、持続可能社会のための化学、御園生誠、村橋俊一編 117-129「グリーン触媒-均一系錯体触媒」 (2011)
  • Author(s): 村橋俊一
  • Total Pages: 250
  • Publisher: 講談社
• [Book] 化学で何ができるか 未来につながる「化学」の架け橋 211-219「グリーンケミストリー」 (2011)
  • Author(s): 村橋俊一
  • Total Pages: 276
  • Publisher: 有機合成化学協会編、化学工業日報社
• [Book] In Oxidation Methods(2nd Ed.J.E.Backvall Ed.)(Ruthenium-catalyzed Oxidation for Organic Synthesis) (2010)
  • Author(s): Shun-Ichi Murahashi, Naruyoshi Komiya
  • Publisher: Wiley-VCH, Weinheim
• [Book] In Electronic Encyclopedia of Reagents for Organic Synthesis(Ed.,L.A.Paquette)(Pentahydridobis (triisopropylphosphine) irid ium(V)) (2010)
  • Author(s): 村橋俊一
  • Publisher: Wiley, New York
• [Book] In Electronic Encyclopedia of Reagents for Organic Synthesis(Ed.,L.A.Paquette)(Dichlorotris (triphenylphosphine) ruthenium (II)) (2010)
  • Author(s): 村橋俊一
  • Publisher: Wiley, New York
• [Book] In Modern Oxidation Methods(Ed.,J.-E.Bachvall)(Ruthenium-Catalyzed Oxidation for Organic Synthesis) (2010)
  • Author(s): Shun-Ichi Murahashi, Naruyoshi Komiya
  • Publisher: Wiley-VCH, Weinheim
• [Book] Modern Oxidation Methods, 2nd Ed.J.E.Backvall Ed.241-268 "Ruthenium-catalyzed Oxidation for Organic Synthesis" (2010)
  • Author(s): Shun-Ichi Murahashi, Naruyoshi Komiya
  • Total Pages: 481
  • Publisher: Wiley-VCH, Weinheim
• [Book] Electronic Encyclopedia of Reagents for Organic Synthesis, Ed., L.A.Paquette, "Dichlorotris(triphenylphosphine)ruthenium(II)" "Pentahydridobis(isopropylphosphine)iridium(V)" (2010)
  • Author(s): Shun-Ichi Murahashi
  • Publisher: Wiley, New York
• [Book] In Asymmetric Synthesis-The Essentials(Ed.,M.Christmann, S.Braese)(Asymmetric Synthesis of Amines and Amino Acids from Amines) (2007)
  • Author(s): Shun-Ichi Murahashi, Yasushi Imada
  • Publisher: Wiley-VCH, Weinheim
• [Book] Asymmetric Synthesis-The Essentials (2007)
  • Author(s): S.I. Murahashi, Y. Imada
  • Publisher: Wily-VCH
• [Remarks]
  • URL: http://www.ous.ac.jp/DAC/otera/murahashi/index.html