钨氧酸盐和有机小分共催化的光照下不对称Michael加成反应

Asymmetric synthesis plays an extremely important role in modern pharmaceutical industry, agrochemistry and material chemistry. Although great progress has been achieved in this field in the past decades, yet significant challenge still exists in developing environmentally friendly and economical asymmetric transformations. Photochemistry reactions can catalyzed many reaction under environment-friendly condition by taking advantage of light energy, and the reaction is easy to handle. However, only few catalytic asymmetric reactions mediated in this field have been reported and much effort is highly desired. This project will merge the inorganic POM photoredox catalyst like W10O324- and chrial Brönsted acid (eg, chiral phosphoric acids) together to explore novel asymmetric transformations. This new strategy can afford many chiral molecules that is hard to be attained by traditional synthetic approaches, and we will apply this novel method to construct important chiral building blocks and bioactive small molecules.

不对称合成在药物开发，农业化学以及材料化学中都有着非常广泛的作用。尽管不对称合成在过去的几十年中得到飞速的发展，但在当前绿色环保且经济适用的背景下，这一领域仍然有着巨大的发展空间。通过利用的是光能，有机光化学反应可以在很温和的条件下进行，具有低能耗易操作等优点。但是目前这一领域尚未在不对称合成中得到充分的发展。本项目将结合无机光敏剂，如钨氧酸盐，和有机小分子催化剂共同作用下实现不对称Michael加成反应，构建一些经典方法难以构建的手性小分子，并应用于手性切块和具有重要生理活性小分子的合成中。

钨氧酸盐作为常见的光敏剂，常用于各种光催化反应，但是其不对称光催化反应的研究较少。我们以手性膦酸为共催化剂，对十聚钨酸负离子催化的不对称Michael加成反应进行了探索。钨酸盐也常用于氧化反应，我们研究了钨酸盐催化的芳胺氧化偶联为偶氮氧及杂芳烃的绿色卤化反应。该反应底物范围广泛，条件温和，我们进一步探讨了该类化合物在药物设计以及天然产物合成的应用。