基于邻位官能化芳基异腈的C-H官能化反应构建若干二苯并氮杂卓衍生物

异腈由于其独特的分子结构在有机串联反应中得到广泛应用。近年来，报道了众多基于异腈的自由基环化反应构建具有生物活性的重要氮杂环，如吲哚、菲啶、喹啉等。二苯并氮杂卓单元，是含七元氮杂环的三并环结构，含该结构单元的相关化合物通常具有良好的生物活性、光电物理性质及潜在应用价值，受到广大化学、医药、生物研究者的关注。现合成二苯并氮杂卓衍生物路线长、效率低，而基于异腈的串联环化法合成未见报道。基于我们前期在C-H官能化、构建含氟杂环、异腈及自由基化学方面的研究，本项目拟开展：钯催化C-H活化官能化，或在自由基引发剂或光照条件下，与易得的含氟烷基、芳基、烷基、酰基、磷酰基、芳基硫醚基和硅基化试剂反应，发展邻位苄基化、醚化、硅基化、磺酰基和亚磺酰基化、膦酰基化异腈的串联氧化加成环化反应。预期将获得若干官能化二苯并氮杂卓、二苯并氧/硫/膦/硅氮杂卓衍生物，以满足新型医药、农药、光电材料等研发需求。

Isocyanides have a broad range of applications in organic cascade reactions due to their unique molecular structures. Recently, various radicals have been widely added to the isocyanide carbon atom to construct some bioactive nitrogen heterocycles, such as indoles, phenanthridines, quinolines and other N-containing heterocycles. As a privileged fragment, dibenzoazepine is a seven-membered fused tricyclic unit. Some attention has been given to the dibenzoazepine derivatives because of their good bioactivity, optical and electrical properties, and potential applications. The present methods for the synthesis of dibenzoazepines are low efficiency, however, the approach based on cascade addition cyclization of isocyanides has not been reported yet. And on the base of our previous work: C-H bond functionalization, construction of F-containing heterocycles, and radical addition cyclization of isocyanides, this project will focus on the synthesis of dibenzoazepine derivatives by Pd-catalyzed C-H bond functionalization, or radical cascade reactions using isocyanides as radical acceptors under the conditions of radical initiator, visible light or LEDs. We will investigate some functional agents containing fluoroalkyl, aryl, alkyl, acyl, phosphoryl, silyl, and arylthiyl groups. The substrates involve ortho-benzylated, etherified, silicified, sulfated, sulfenylated, and phosphonylated isocyanides. We will expect to obtain some functionalized dibenzoazepines, and some other O-/S-/P-/Si-containing dibenzoazepines, to promote the development of new pharmaceuticals, pesticides, photoelectric materials, and etc.