模拟细胞色素P-450的仿生氧化反应的研究 T.氯合5,10,15,20-四苯基卟吩合铁(III)催化下不同亚碘酰芳烃及其衍生物的结构对环己烷充氧化反应的影响

Study of Biomimetic Oxidation Catalyzed by the Model Compound of Cytochrome P-450 Ⅰ. The Influence of the Structure of Some Substituted Iodosobenzene and Iodosobenzene Derivatives on the Oxygenation of Cyclohexane Catalyzed by 5,10,15, 20-Tetraph

在氯合5,10,15,20-四苯基卟吩合铁(Ⅲ)[TPPFe(Ⅲ)Cl]催化下,带有不同取代基的亚碘酰苯和亚碘酰苯的衍生物作充氧化剂对环己烷进行了仿生单充氧化反应的研究.取代亚碘酰苯中对位取代基的电子效应和间位取代基的电子及立体效应对氧化产物环己醇的产率有良好线性相关性.

The biomimetic monooxygenation of cyclohexane with some substituted iodosobenzene and iodosobenzene derivatives catalyzed by 5,10,15,20-tetraphenylporphinatoiron chloride[TPPFe(Ⅲ)Cl]was studied.The electronic effect of para substituents and both the steric and electronic effect of meta substituents in the substituted iodosobenzene were well linear correlated to the yields of cyclohexanol.When either phenyliodosyldiacetate or phenyliodosyltosylate was used as oxidant,the yields of cyclohexanol were low,close to the case when iodosobenzoic acid or o-iodosobenzoic ester was used(near to zero).All these compounds were much weaker oxidants than iodosobenzene.It may be suggested that the intermolecular and intramolecular bonding structure-I(OH)OCO-iniodosobenzoic acid and o-iodosobenzoic ester were present.Besides,the effects of the structure of oxygen donor[I=O or I(OA)OB]to the activity of oxygenation was discussed.