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

基于具有双环骨架的手性扩展N-杂环卡宾的不对称烯烃复分解催化剂

• 批准号: 404839265
• 负责人: Professor Dr. René Wilhelm
• 金额: --
• 依托单位: Institut für Organische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2018
• 资助国家: 德国
• 起止时间: 2017-12-31 至 2021-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/404839265?language=en
• 关键词: Asymmetric; olefin; metathesis; catalysts; based

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.

总之，本项目涉及基于具有双环框架的手性扩展的N-杂环卡宾的新型手性Grubbs-Hoveyda II催化剂的开发。卡宾前体可以由樟脑在几个步骤中制备，虽然在卡宾中只有一个手性骨架，但由于引入了不同的侧臂，这些卡宾的几种修饰将是可能的。利用异辛酸合成了主链上具有手性信息的六元环卡宾。Grubbs-Hoveyda II催化剂与这些卡宾的一些类似物已经被证明在不对称开环交叉复分解中产生不对称诱导。一个新的配合物的主要研究将在不对称环重排复分解（ARRM）。到目前为止，大多数RRM的例子已经用非手性催化剂进行。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。