2006 Fiscal Year Final Research Report Summary
Explaitation of Environmentally Benig Biomimetic Catalytic Oxidation Reaction
| Project/Area Number |
17550110
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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 Univeristy of Science |
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Principal Investigator |
MURAHASHI Shun-ichi Okayama Univerity of Science, Department of Chemistry, Professor, 客員教授(常動扱) (60029436)
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| Project Period (FY) |
2005 – 2006
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| Keywords | Flavin catalyst / Aerobic oxidation of sulfide / aerobic Baeyer Villiger oxidation / Ruthenium catalyst / Oxidative cyanation of amine / Oxidation with hydrogen peroxide / Aminonitrile / C-H activation |
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| Research Abstract |
Aerobic oxidation of organic compounds under mild reaction conditions is one of the most difficult problems to be solved. By simulation of the function of flavoenzyme we found that aerobic oxidation of sulfides and secondary 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, and the by-products are water and molecular nitrogen, which are environmentally benign. We clarified the mechanism. Furthermore, we found that flavin catalyzed Baeyer-Villiger oxidation of ketones occurs in the presence of zinc highly efficiently at room temperature under molecular oxygen (1 atom). An important feature of this new method is the chemoselective oxidation of ketones in the presence of other reactive functionalities, such as olefins and sulfides.
We also extended our work on the simulation of the function of cytochrome-P450 with ruthenium catalysts. We found that aerobic oxidative cyanation of tertiary amines with NaCN occurs in the presence of ruthenium trichloride catalyst under molecular oxygen (1 atom) to give a-aminonitriles, which are versatile intermediates for synthesis of a-amino acids and 1,2-diamines. Based on the precise mechanistic study, we found that similar oxidative cyanation also occurs upon treatment of tertiary amines with hydrogen peroxide selectively. In addition, we found that new type of enatio-selective, direct oxidations of alkanes with the manganese catalyst bearing a binaphthyl strapping unit and selective oxidation of olefin with binapthyl ruthenium catalysts are explored.
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