Catalytic methods for peroxide mediated oxidation

我们最近报道了一种在湿气和空气存在下进行烯烃二羟基化的无金属方法（J. Am. 2010，132，14409）。用一当量的过氧化丙二酰（CHCl 3; 0.5M;室温; H2O 1当量），然后水解，以82-96%的分离产率和顺式选择性（高达50：1）得到相应的二醇。这是一种有效的烯烃双羟基化方法，与传统的过渡金属催化方法相比具有显著的优势，具有很大的发展潜力。为了实现这一议定书的全部潜力，必须开发一种催化程序。因此，我们希望开展一个具有以下主要目标和目的的项目：* 开发一种用于烯烃二羟基化的新型催化循环。确定取代烯烃的工艺范围。表征催化循环的动力学和机理。该项目的成功结果将提供一种简单，有效和工业相关的催化氧化过程，该过程在室温下在水分和空气存在下进行。

The project will involve development of synthetic methodology guided by mechanistic insight of importance to the thematic areas of Healthcare Technologies, Physical Sciences and Manufacturing the Future.We have recently reported a metal-free method for the dihydroxylation of alkenes that proceeds in the presence of both moisture and air (J. Am. Chem. Soc. 2010, 132, 14409). Treatment of an alkene with one equivalent of a malonoyl peroxide (CHCl3; 0.5 M; r.t.; H2O 1 equiv), followed by hydrolysis, gives the corresponding diol in 82-96% isolated yield with syn selectivity (up to 50:1). This represents an effective method for the dihydroxylation of alkenes which has significant advantages over traditional transition-metal catalysed processes and has great potential for development. In order to realise the full potential of this protocol a catalytic procedure must be developed. We therefore wish to undertake a project with the following major goals and objectives:* Develop a novel catalytic cycle for the dihydroxylation of alkenes.* Establish the scope of the process for substituted alkenes.* Characterise the kinetics and mechanism of the catalytic cycle.Successful outcome of this project will deliver a simple, effective and industry relevant catalytic oxidation procedure that proceeds at room temperature in the presence of moisture and air.