模拟细胞色素P-450的仿生氧化反应的研究 I: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

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. 亚碘酰苯的衍生物苯亚碘酸二醋酐与苯亚碘酸单对甲苯磺酸酐对环己烷的充氧化能力和邻、间、对亚碘酰苯甲酸与邻亚碘酰苯甲酸酯相似, 环己醇产率接近零. 从而提出亚碘酰苯甲酸及邻亚碘酰苯甲酸酯存在分子内或分子间I(oh)oco成键结构的论点.

Study of biomimetic oxidation catalyzed by the model compound of cytochrome P-450 I: The influence of the structure of some substituted iodosobenzene derivatives on the oxygenation of cyclohexane catalyzed by 5,10,15,20-tetrapenylporphinatoiron chloride

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 phenyliodosyl diacetate or phenyliodosyl tosylate 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 intermol. and intramol. bonding structure-I(OH)OCO- in iodosobenzoic acid and o-iodosobenzoic ester were present. Besides, the effects of the structure of oxygen donor to the activity of oxygenation was discussed.