| Project/Area Number |
08555223
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 展開研究 |
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| Research Field |
有機工業化学
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| Research Institution | Osaka University |
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Principal Investigator |
MURAHASHI Shun-Ichi Department of Chemistry, Graduate School of Engineering Science, Osaka University Professor, 大学院・基礎工学研究科, 教授 (60029436)
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| Co-Investigator(Kenkyū-buntansha) |
ODA Yoshiaki Sumitomo Chemical Co.Researcher, 技術室, 研究員(研究職)
TAKAYA Hikaru Department of Chemistry, Graduate School of Engineering Science, Osaka Univertis, 大学院・基礎工学研究科, 助手 (50304035)
KOMIYA Naruyoshi Department of Chemistry, Graduate School of Engineering Science, Osaka Universit, 大学院・基礎工学研究科, 助手 (00301276)
IMADA Yasushi Department of Chemistry, Graduate School of Engineering Science, Osaka Universit, 大学院・基礎工学研究科, 助教授 (60183191)
NAOTA Takeshi Department of Chemistry, Graduate School of Engineering Science, Osaka Universit, 大学院・基礎工学研究科, 助教授 (20164113)
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| Project Period (FY) |
1996 – 1998
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| Keywords | Oxidation of Alkanes / Aerobic Oxidation / Oxidation of Cyclohexane / Oxidation of Amines / Oxidation of Amides / Ruthenium Catalyst / Copper Catalyst / Peroxides |
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| Research Abstract |
The main aim of the present research project is to acquire innovative method for biomimetic oxidative transformations of unreactive organic substrates and to extend it to the organic syntheses and industrial processes. Based on the new strategy for simulating enzymatic function of cytochrome P-450 monooxygenases with transition metal catalysts, the generation, reactivity and catalysis of various oxometal species of transition metals have been investigated from synthetic viewpopints. Oxoruthenium species generating from low valent ruthenium complexes and peroxides such as t-BuOOH and AcOOH has proven to be highly reactive catalytic species for the oxidations of unreactive substrates. Thus, a variety of specific oxygenation reactions of amines, amides, phenols and alkanes can be performed with ruthenium catalysts with peroxides. These new reactions provides a powerful synthetic method for transformations of unreactive substrates, including biomimetic cyclization of aminoolefins, alpha-substitution of amines, and quinone synthesis from phenols. Extension of the principle of the generation of oxometal species has led to the novel aerobic oxidations in the presence of aldehydes. Aerobic oxidation of alkanes can be performed efficiently under mild conditions in the presence of a catalytic amount of low valent transition metal catalysts and aldehydes. As a consequence of further study focused on the oxidation of industrially important cyclohexane, extremely high efficiency and selectivity have been achieved using CuCl_2-crown ethers or ruthenium fluorinated porphyrin ruthenium complexes as a catalyst.
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