2004 Fiscal Year Final Research Report Summary
Exploitation of Catalytic Biomimetic Oxidation Reaction
| Project/Area Number |
15550097
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Okayama University of Science |
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Principal Investigator |
MURAHASHI Shun-ichi Okayama University of Science, Professor, 客員教授(常勤) (60029436)
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| Co-Investigator(Kenkyū-buntansha) |
ORITA Akihiro Okayama University of Science, Department of Applied Chemistry, Associate Professor, 工学部, 助教授 (30262033)
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| Project Period (FY) |
2003 – 2004
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| Keywords | biomimetic, green oxidation / aerobic oxidative cyanation of tertiary amines / ruthenium catalyst / aerobic flavin catalyzed oxidation of sulfides / flavin catalyst / synthesis of α-amino acides / aerobic hydroxylation of hydrocarbons. / enantioselective oxidation of hydrocarbon |
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| Research Abstract |
Exploitation of biomimetic catalytic oxidation gives fundamental, green processes. The aerobic oxidation of organic compounds under mild reaction conditions is one of the difficult problems to be solved. By simulation of the function of flavoenzyme we found that the aerobic oxidation of sulfides, secondary amines, tertiary amines, and N-hydroxyl amines is performed in the presence of 5-ethyl-3methylflavinium perchlorate catalyst and hydrazine hydrate at room temperature highly selectively The turn-over number (TON) is 19,000. The by-products are water and molecular nitrogen, which are environmentally benign. We also extended our work on the simulation of the function of cytochrome-P450, and we found that aerobic oxidation and the carbon-carbon bond formation occurs at once under mild reaction conditions. Thus, the reaction of tertiary amines with NaCN in the presence of RuCl3 catalyst in methanol-acetic acid under molecular oxygen (1 atom) gave α-aminonitriles, which are versatile intermediates for synthesis of a-amino acids and 1,2-diamines, highly efficiently. The enatioselective, direct oxidations of alkanes and alkenes are extremely difficult tasks ; however, we succeed in obtaining alcohols and epoxides with high enantioselectivity.
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