| Project/Area Number |
02403019
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| Research Category |
Grant-in-Aid for General Scientific Research (A)
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| Allocation Type | Single-year Grants |
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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 Osaka Univ.,Fac.of Eng.Sci. Professor, 基礎工学部, 教授 (60029436)
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| Co-Investigator(Kenkyū-buntansha) |
IMADA Yasushi Osaka Univ.,Fac.of Eng.Sci. Assistant, 基礎工学部, 助手 (60183191)
NAOTA Takeshi Osaka Univ.,Fac.of Eng.Sci. Assistant, 基礎工学部, 助手 (20164113)
HOSOKAWA Takahiro Osaka Univ.,Fac.of Eng.Sci. Associate Professor, 基礎工学部, 助教授 (90029520)
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| Project Period (FY) |
1990 – 1992
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| Project Status |
Completed (Fiscal Year 1992)
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| Budget Amount *help |
¥36,500,000 (Direct Cost: ¥36,500,000)
Fiscal Year 1992: ¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 1991: ¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 1990: ¥28,500,000 (Direct Cost: ¥28,500,000)
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| Keywords | Ruthenium complexes / Catalytic oxidation / Oxidation of amines / Oxidation of amides / Oxidation of hydrocarbons / Hydration of nitriles / C-H activation / 低原子価ルテニウム錯体 / 酸素酸化 / オレフィンの酸化 / アルカンの酸化 / オスミウム錯体 / 第3アミン / βーラクタム / イミニウムイオン中間体 / フラビン / 酸化反応 / アルド-ル型反応 / アミド / ニトリル |
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| Research Abstract |
Low valent transition metal complexes,particularly ruthenium complexes are of interest,because ruthenium complexes have various oxidation states(from Ru(-II) to Ru(VIII))and strong coordination ability to oxygen and nitrogen atoms. Concerning to low valent ruthenium complex catalyst,we have investigated three type of reactions. 1)Cytochrome P-450 type oxidation. 2)Lewis acid promoted reaction. 3)C-H activation of nitrile. 1. Ruthenium-catalyzed reaction of teriary N-methylamines with t-butyl hydroperoxide gives the corresponding alpha-(t-butyldioxy)methylamines highly efficiently. The kinetic experiments indicate that the present reaction proceeds via Cytochrome P-450 type mechanism,which involves oxo-ruthenium(IV) species as a key intermediates. The oxidation of amides and lactams with peroxides also proceeds under mild reaction conditions to give the oxygenated products. Similar treatment of beta-lactams with peracetic acid affords beta-acetoxy-beta-lactams which are key intermediate
… More
s for the synthesis of carbapenem antibiotics. By using these catalytic systems,direct oxidation of hydrocarbons can be performed to give the corresponding alcohols and ketones. 2. Ruthenium-catalyzed hydration of nitriles proceeds highly efficiently upon treatment with only equimolar amount of water under neutral conditions. Extension of the principle of the amide formation disclosed novel catalytic transformations of nitriles. Thus,ruthenium-catalyzed condensation of nitriles with amines in the presence of two equivalents of water gives the corresponding amides along with evolution of ammonia. The efficiency of the present process is highlighted by the synthesis of various industrially important polyamides. The ruthenium-catalyzed reaction of dinitriles with diamines in the presence of water gives polyamides, generally. Aminonitriles undergo similar polycondensation efficiently. 3. The ruthenium-catalyzed aldol-type condensation of nitriles with carbonyl compounds proceeds under mild and neutral conditions. Under the similar reaction conditions,nitriles react with alkenes bearing electron withdrawing group to give the corresponding Michael adducts. One important feature of the present reactions is the chemoselective reaction of nitriles with carbonyl compounds or Michael acceptors in the presence of other active methylene compounds. Less
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