Asymmetric olefin metathesis catalysts based on chiral extended N-heterocyclic carbenes with a bicyclic framework

综上所述，本项目涉及基于双环框架的手性扩展n杂环碳烯的新型手性Grubbs-Hoveyda II催化剂的开发。碳烯前体可以通过几个步骤从樟脑中制备出来，尽管在碳烯中只提出了一个手性骨架，但由于引入了不同的侧臂，这些碳烯将有可能进行几种修饰。樟脑酸的应用为合成具有手性信息的六元环碳烯提供了一条简单的途径。一些含有这些碳烯的Grubbs-Hoveyda II型催化剂的类似物已经被证明在不对称开环交叉复分解中具有不对称诱导作用。新的配合物的主要研究方向是不对称环重排复合（ARRM）。到目前为止，大多数RRM的例子都是用非手性催化剂进行的。通过这种串联反应，可以直接获得与天然和非天然产物相关的对映体富集形式的复合物结构。

In summary, this project deals with the development of new chiral Grubbs-Hoveyda II catalysts based on chiral extended N-heterocyclic carbenes with a bicyclic framework. The carbene precursors can be prepared in a few steps from camphor and although only one chiral backbone in the carbenes is proposed, several modifications of these carbenes will be possible due to the introduction of different sidearms. The application of camphoric acid provides an easy route to six-membered ring carbenes with chiral information in the backbone. Some analogues of Grubbs-Hoveyda II catalysts with these carbenes have already proven to give asymmetric induction in the asymmetric ring opening cross metathesis. A major investigation of the new complexes will be in the asymmetric ring-rearrangement metathesis (ARRM). So far, most examples of RRM have been carried out with achiral catalysts. Via this tandem reaction complex structures could be directly available in enantioenriched form relevant for natural and non-natural products.