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Chiral model complexes for methane monooxygenase and their asymmetric catalysis of styrene epoxidation
引用本文:魏俊发,俞贤达,金道森. Chiral model complexes for methane monooxygenase and their asymmetric catalysis of styrene epoxidation[J]. 中国科学B辑(英文版), 1998, 41(3): 247-254. DOI: 10.1007/BF02879703
作者姓名:魏俊发  俞贤达  金道森
作者单位:Lanzhou Institute of Chemical Physics,Chinese Academy of Sciences,Lanzhou 730000,China
摘    要:
Asymmetricsynthesis,inparticularthecatalyzedasymmeticsynthesis,hasbeenafascinatingareaofcurrentresearchinterestduetospecialphysicologicalactivitiesandwideapplicationsasmedicinesandpesticides[1].Asymmetriccatalyst,whichpresentsachiraltemplate,playsacrucia…

收稿时间:1997-09-18

Chiral model complexes for methane monooxygenase and their asymmetric catalysis of styrene epoxidation
Junfa Wei,Xianda Yu,Daosen Jin. Chiral model complexes for methane monooxygenase and their asymmetric catalysis of styrene epoxidation[J]. Science in China(Chemistry), 1998, 41(3): 247-254. DOI: 10.1007/BF02879703
Authors:Junfa Wei  Xianda Yu  Daosen Jin
Affiliation:(1) Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, 730000 Lanzhou, China
Abstract:
Four chiral π-phenolato dinuclear (VO)2, Cr2, Mn2, and Fe2 complexes with a phenolic ligand bearing two L-phenylanalines as complexing arms have been synthesized and characterized. Asymmetric epoxidations of styrene with these complexes as chiral models of methane monooxygenase (MMO) and iodosylbenzene as an oxygen atom donor have been studied. The results reveal that the Mn2, complex catalyzes asymmetric epoxidation of styrene with the formation of R-(+)-styrene oxide in 42.8% e. e. Contrarily, the (VO)2 analogue complex gives S-(-)-styrene oxide in 19.2% e.e. EPR investigations suggest that the catalyzed epoxidations with the Mn2, Cr2 and Fe2 complexes proceed via high-valent oxometal intermediates; while in the case of the (VO)2 complex as catalyst, the epoxidation proceeds by a pathway that involves a complex of metal-iodine ligand. The catalytic activities of the complexes decrease in a sequence of Mn2>Cr2>(VO)2> Fe2.
Keywords:methane monooxygenase   dinuclear complex   mimick enzyme   epoxidation   asymmetric catalysis   biomimetic catalysis.
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