创建远程脱氢官能团化技术催化合成环共轭二烯和芳香族化合物

远程官能团化技术是近年来最为热门的研究领域之一，它提供了许多有趣的应用，并能使简单的原料增加其应用价值。然而，远程环内脱氢烯基化技术以及相关的异构化反应还相对滞后，这落差很大程度上降低了共轭环二烯和芳基等产品的供应，结果制约了以那些重要的化学品为原料的各种各样的发展。.目前，那些重要的化学品仍以非常传统的方法合成。它们仍然严重依赖环内烯底物的供应、经常要使用缺电子的基团协助进行，或需使用高温、强碱及氧化剂等苛刻条件，不利于大规模生产，其适用范围也受限制。.我们组最近以氢烯基化过渡金属催化剂发现了一种有效的亚甲基环丙烷碳骨架重排活化的新方法。在这个项目上，它启发了我们研究及利用烯基化催化剂进行环内烯丙基位的活化重排。在结合我们长期关注的氢烯基化反应技术知识后，我们计划发展可以从简单的远程环外烯出发的反应技术，一步绿色地进行链走、环外到内烯异构化、脱氢芳构化和共轭环二烯化，促进相关产业的发展。

Remote functionalization is a hot topic in recent years, it offers a number of interesting applications, and provides value-added raw materials. However, the related development in remote dehydro-functionalization of cyclic compound is rather lag behind. This has lowered the availability of new conjugated endocyclic dienes and aromatic compounds, and consequently limited those vast developments relying on them..Currently, those important chemicals are still prepared by using traditional methods. They heavily depend on the production of endocyclic alkenes, and frequently require the assistance of electron-deficient activators, or need to run the reaction at high temperature, strong base and oxidant conditions, which are difficult for larger scale production and limited the scope of this type of technology. .Our group recently has discovered a new method to catalyze methylenecyclopropane C-C framework rearrangement by using alkenylation catalyst. In this project, that inspired us to use such catalyst for endocyclic allylic rearrangement. By combining our knowledge in alkenylation, we plan to develop a remote dehydro-functionalization method that using remote exocyclic olefin as substrate. Conjugated endocyclic dienes and aryls will be obtained in 1 step by chain-walking, exo-to-endo isomerization and CH activation under green and catalytic condition.