Development of selective oxygenation of nonactivated hydrocarbons by iron catalysts

从催化的角度研究了加氧酶模型非血红素铁配合物对非活性烃的催化氧化作用，并广泛研究了铁（III）配合物对邻苯二酚的选择性二醇内氧化作用。在这个项目中，第一个例子的催化氧化氯邻苯二酚模型铁配合物已经实现。这不仅是氯邻苯二酚双加氧酶的第一个模型反应，而且是开发环境污染物卤代芳烃分解的第一步，是非常重要的结果。分离出了模型中间体--氯代血红素铁-（TPA）配合物，并用XAFS分析了它们的结构，研究了另一个双加氧酶模型反应--非血红素铁配合物催化的脂氧合酶模型反应。自由基中间体的ESR检测，支持自由基机制提出的酶体系。单加氧酶模型反应也进行了研究，特别是通过使用氢醌作为电子和质子转移试剂。在这个项目中，选择性邻羟基化的酚铁（III）配合物已被开发，作为酪氨酸羟化酶的模型反应。具体而言，对苯二酚上的取代基对控制反应性起着至关重要的作用。

Catalytic oxygenation of nonactivated hydrocarbons by oxygenase-model nonheme iron complexes has been studied from the viewpoints of catalysis.Selective intradiol oxygenation of catechols by iron (III) complexes has been extensively studied. In this project the first example of catalytic oxygenation of chlorocatechols by model iron complexes has been achieved. This is very important result not only as the first model reaction for chlorocatechol dioxygenases, but also for the first step of development of decomposition of haloaromatics which are environmental pollutant. The model intermediate complexes, chlorocateholaoiron - (TPA) complexes have been isolated, and their structures were analyzed by XAFS.Another dioxygenase model reaction, i.e.lipoxygenase model reaction catalyzed by nonheme iron complexes, has been studied. Radical intermediates were detected by ESR,supporting the radical mechanism proposed in the enzymatic systems.Monooxygenase model reactions have also been studied, specially by using hydroquinones as electron and proton transfer reagents. In this project, selective ortho-hydroxylation of phenols by iron (III) complexes has been developed, as an model reaction for tyrosine hydroxylase. It is specific that substituents on hydroquinones play essential role for controlling reactivity.