不对称Heck/去对称化反应研究及其在手性桥环化合物合成中的应用

手性桥环骨架在活性分子中广泛存在，也是重要的合成砌块之一，其合成已日益受到重视。然而由于桥环张力和多个手性中心的存在，桥环骨架的构建及立体选择性控制变得十分困难。因此如何高效构筑桥环骨架、如何控制立体选择性成为多手性中心桥环化合物合成亟待解决的关键科学问题。课题组前期工作中开发了催化不对称Heck/去对称化反应，实现了多取代桥环骨架的不对称合成，在此基础上，本项目以多手性中心桥环化合物为研究对象，针对手性桥环骨架的不对称合成中的关键科学问题，进一步发展催化不对称Heck（类Heck）/去对称化反应方法，阐明其反应规律，进而利用本项目发展的催化不对称Heck（类Heck）/去对称化反应新策略，开展系列手性桥环的构建，并拓展其在活性分子的结构修饰和合成应用。期待通过本项目的实施，开发出手性桥环骨架的不对称合成方法，从而为高效构建含有手性桥环骨架结构的活性分子合成和结构修饰奠定一定的化学基础。

As one of the most prevalent groups of bioactive compounds and one of the most important buiiding blocks, the preparation of bridged skeletons has attracted much attention in the synthetic community over the last few decades. Although many methods have been developed for the enantioselective construction of the bridged frameworks, how to effciently build bridged frameworks and how to control the regioselectivity still remains big challenges for synthetic chemists due to the existence of multiple chiral centers. In the past two years, We have developed an asymmetric Heck/desymmetrization reaction of cyclopentenes for the construction of chiral bicyclo[3.2.1]octanes in excellent enatioselectivities. This proposal is aimed to further investigate assymetric Heck(or Heck type)/desymmetrization reactions and their synthetic application to preparation of the bridged skeletons and chiral bioactive compounds bearing multiple substituted groups.