SYNTHESIS OF ASYMMETRIC PORPHYRIN AND ENANTIOSELECTIVE OXYGENATION USING CHIRAL PORPHYRIN IRON COMPLEX
| Project/Area Number |
62470082
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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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 | DOSHISHA UNIVERSITY |
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Principal Investigator |
HASHIMOTO Shizunobu DOSHISHA UNIVERSITY, PROFESSOR, 工学部, 教授 (90066027)
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| Co-Investigator(Kenkyū-buntansha) |
TAMARU Yoshinao KYOTO UNIVERSITY, ASSOCIATE PROFESSOR, 工学部, 助教授 (80026319)
KANO Koji DOSHISHA UNIVERSITY, PROFESSOR, 工学部, 教授 (60038031)
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| Project Period (FY) |
1987 – 1988
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| Project Status |
Completed (Fiscal Year 1988)
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| Budget Amount *help |
¥7,800,000 (Direct Cost: ¥7,800,000)
Fiscal Year 1988: ¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 1987: ¥4,600,000 (Direct Cost: ¥4,600,000)
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| Keywords | model of cytochrome P-450 / alkene / oxygenation / reaction mechanism / optically active amine / asymmetric oxygenation / bovin serum albumin / 水溶性ポルフィリン / チトクロームPー450モデル / 酸素化反応 / 水溶性ポルフィリン錯体 / 鉄テトラフェニルポルフィン / チトクロームPー450 / スチレン / 環状アルケン / 1ーフェニルエタノール / ベンジルアルコール |
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| Research Abstract |
The oxygenation of various alkenes using Fe(III)tetraphenylporpine (FeTPP) as a catalyst has been studied in benzene-ethanol containing NaBH_4 and diphenyl-disulfide. The final products are the alcohols and the reactoins can be regarded as the addition of H_2O to the alkenes which follows a Markovnikov's rule. The detailed study on the oxygenation of styrene suggests the reaction mechanism involving reduction of Fe(III)TPP to Fe(II)TPP by BH^-_, coordination of O_2 to Fe(II)TPP, formation of dioxetane of styrene, hydride reduction of the dioxetane to yield acetophenone and benzaldehyed, and reduction of these carbonyl compounds by BH^-_. The proposed mechanism indicates that the enantioselective oxygenation of alkenes catalyzed by an asymmetric Fe-porphyrin cannot be realized in this system. Then we have examined the oxygenation of optically active schiff bases of 2-methylcyclohexanone. The reactions of the schiff bases in toluene containing Fe(III)TPP, 4-methoxyphenol, and CaH_2 and the hydrolyses provide 2-hydroxy-2-methylcyclonexanone in low optical yields (0-26 %e.e.). In order to improve the cytochrome P-450 model system, the formation of the complexes of water-soluble porphyrins and bovine serum albumin (BSA) has been tested. BSA forms the stable complexes with cationic porphyrins. Such system may be used as an artificial cytochrome P-450.
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Report
(3 results)
Research Products
(9 results)
