Activation of dioxygen by copper complexes in water for the selective oxidation/oxygenation of organic substrates

有机底物如环己烷的选择性氧化在化学工业和实验室中都是极其重要的。到目前为止，许多这些反应都是在有机溶剂中进行的，使用的氧化剂往往是有毒或对环境有害的，和/或昂贵的贵金属催化剂。此外，在大多数情况下，有必要在更高的温度和压力下进行这些反应。相比之下，金属酶，通常是活性部位含有铁或铜离子的单加氧酶，能够在环境条件下，以空气中的氧气为氧化剂，在水中执行这些反应。模型化合物已被用来模拟这些酶的反应活性，但到目前为止，氧化/氧化反应主要在有机溶剂中进行。对于工业应用，存在形成有机溶剂和氧气的爆炸性混合物的危险，这可能会导致火灾甚至爆炸。在这个项目中，铜的络合物应该以这样的方式进行修饰，以便能够在水中以氧气作为唯一的氧化剂进行有机底物的氧化/氧化反应。

Selective oxidations of organic substrates such as e. g. cyclohexane are extremely important in chemical industry and in the laboratory. Up to now many of these reactions are performed in organic solvents applying oxidants that often are toxic or bad for the environment and/or expensive catalysts based on noble metals. Furthermore, most of the time it is necessary to run these reactions at higher temperatures and pressures. In contrast metalloenzymes, often monooxygenases with iron or copper ions at the active site are capable to perform these reactions under ambient conditions in water with dioxygen from air as an oxidant. Model compounds have been applied to mimic the reactivity of these enzymes, however, so far the oxidation/oxygenation reactions mainly were performed in organic solvents. For applications in industry there is the danger of the formation of explosive mixtures of organic solvents and dioxygen, that can lead to a fire or even an explosion. In this project copper complexes should be modified in such a way that it will be possible to perform oxidation/oxygenation reactions of organic substrates in water with dioxygen as the sole oxidant.