Exploitation of Catalytic Biomimetic Oxidation Reaction

仿生催化氧化的开发提供了基本的、绿色的过程。有机化合物在温和反应条件下的好氧氧化是有待解决的难题之一。通过对黄酶功能的模拟，发现在5-乙基-3甲基高氯酸黄盐催化剂和水合肼存在下，硫化物、仲胺、叔胺和n-羟基胺在室温下进行了高选择性的好氧氧化，周转率（TON）为19000。副产品是水和氮分子，对环境无害。我们还扩展了我们对细胞色素p450功能的模拟工作，我们发现在温和的反应条件下，有氧氧化和碳-碳键的形成同时发生。因此，叔胺与NaCN在RuCl3催化剂存在下，在甲醇-乙酸中，在分子氧（1原子）作用下反应得到α-氨基腈，这是合成a-氨基酸和1,2-二胺的多功能中间体。烷烃和烯烃的直接氧化是一项极其困难的任务；然而，我们成功地得到了具有高对映选择性的醇和环氧化物。

Exploitation of biomimetic catalytic oxidation gives fundamental, green processes. The aerobic oxidation of organic compounds under mild reaction conditions is one of the difficult problems to be solved. By simulation of the function of flavoenzyme we found that the aerobic oxidation of sulfides, secondary amines, tertiary amines, and N-hydroxyl amines is performed in the presence of 5-ethyl-3methylflavinium perchlorate catalyst and hydrazine hydrate at room temperature highly selectively The turn-over number (TON) is 19,000. The by-products are water and molecular nitrogen, which are environmentally benign. We also extended our work on the simulation of the function of cytochrome-P450, and we found that aerobic oxidation and the carbon-carbon bond formation occurs at once under mild reaction conditions. Thus, the reaction of tertiary amines with NaCN in the presence of RuCl3 catalyst in methanol-acetic acid under molecular oxygen (1 atom) gave α-aminonitriles, which are versatile intermediates for synthesis of a-amino acids and 1,2-diamines, highly efficiently. The enatioselective, direct oxidations of alkanes and alkenes are extremely difficult tasks ; however, we succeed in obtaining alcohols and epoxides with high enantioselectivity.