金催化的重氮官能团化反应研究

Transitional metal catalyzed carbene transformations from diazo compounds play a vital role in organic synthesis. Generally, the metal complexes of rhodium, copper and palladium have been widely investigated in diazo chemistry. In contrast, much less investigations have been focused on the utilization of gold complexes in diazo involved carbene transfer. Moreover, recent reports and our own investigations revealed that gold complexes displayed dramatically different chem-selectivity compared with the well-known metals such as rhodium, copper and palladium, etc. Meanwhile, metal-catalyzed N-H bond insertion from diazo compounds is a powerful tool to construct C-N bonds, especially in chem- and enantioselective pathway. Thus, to find or develop an efficient approach is highly desired. However, although N-H insertions have been widely investigated, to our knowledge, the utilizations of N-containing heterocyclic compounds as NH precursors for the N-H bond insertions have not been reported. In this program, we will investigate the use of gold complexes as potential catalysts in N-H bond insertions between diazo substrates and N-containing heterocycles. With a view to developing a practical and efficient approach towards the synthesis of chiral N-containing heterocycles, which are common key building blocks in lots of natural products and pharmaceuticals as well as leading compounds. Next, we will investigate the use of gold complexes in a tandem process of cross-coupling of diao and alkyne-amine substrates. In order to develop an efficient methodology to build N-containing heterocycles, polycyclic compounds as well.

过渡金属催化的基于重氮卡宾的官能团转换在有机合成中具有重要的作用。金属化合物如铑、钌、铜、钯等已经被广泛运用到重氮化学的各种反应中。相对来讲，用金化合物催化重氮反应的种类还不多。最近的研究和我们课题组的工作发现金催化的重氮反应也展现出了和常规金属完全不同的化学选择性和区域选择性等。传统的基于重氮卡宾的N-H键插入反应用铑、铜、钯等金属都可以实现，但是用含氮杂环完成N-H键和重氮底物的插入反应用以上金属还不能实现。我们首先将完成金催化的杂环和重氮底物的N-H键插入反应。我还还将完成金催化的胺炔和重氮底物的选择性偶联/环化的串联反应，为含氮杂环、多环的合成设计和发展出一条有效的途径。.本项目将推动金催化剂在卡宾化学的广泛应用，从而推动卡宾化学的发展，并有望发展高效、新颖的合成方法，也将为药物研发和天然产物的合成提供方便简单的含氮杂环砌块。

本项目为金催化的重氮官能团化反应研究(21572024)。过渡金属催化的基于重氮卡宾的官能团转换在有机合成中具有重要的作用。金属化合物如铑、钌、铜、钯等已经被广泛运用到重氮化学的各种反应中。相对来讲，用金化合物催化重氮反应的种类还不多。最近的研究和我们课题组的工作发现金催化的重氮反应也展现出了和常规金属完全不同的化学选择性和区域选择性等。传统的基于重氮卡宾的N-H键插入反应用铑、铜、钯等金属都可以实现，但是用含氮杂环完成N-H键和重氮底物的插入反应用以上金属还不能实现。我们首先将完成金催化的杂环和重氮底物的N-H键插入反应。我还还将完成金催化的胺炔和重氮底物的选择性偶联/环化的串联反应，为含氮杂环、多环的合成设计和发展出一条有效的途径。我们在此期间发表了第一单位通讯论文包括: 3篇Angew. Chem. Int. Ed. ，1篇Chem. Sci., 16篇Org. Lett., 5篇Chem. Commun.等三十篇SCI论文。