基于有机小分子胺催化剂与光催化剂的双催化体系对不饱和羰基化合物的远程不对称催化研究

Recently the dual catalytic system has been attracting considerable attention as it can realize many reactions, which are not easily realized by either conventional reactions or single catalytic system. At present, asymmetric catalytic functionalization of carbonyl compounds by a dual catalytic system that combines organic aminocatalysis and photoredox catalysis only limited at α and β position. We will design and synthesis chiral bifunctional framework catalysts combining proline and BINOL structure, aminocatalysis, chiral phosphoric acid, the dual catalytic system combines with photoredox catalysis and organocatalysis, which contributes a strategy for the direct, stereoselective γ, δ, and ε-functionalization of unsaturated carbonyl compounds. This programe will have profound significance for the dual catalytic system and remote stereocontrol of unsaturated carbonyl compounds.

双催化体系以能实现一些常规反应或单催化体系难以实现的化学反应而受到广泛关注，有机小分子胺催化剂与光催化剂相结合的双催化体系对羰基化合物的不对称催化反应目前只限于其α和β位。申请人拟设计合成基于脯氨酸跟联二萘酚作为手性骨架的双功能催化剂，以及小分子胺或磷酸催化剂与光催化剂相结合的双催化体系，开展对不饱和羰基化合物γ、δ、ε位进行远程手性官能团化研究。本项目的成功实现，对双催化体系以及不饱和羰基化合物的远程立体控制具有重要的研究意义。

本项目在有机小分子催化剂跟光催化剂相结合的双催化体系对不饱和羰基化合物的官能团化的基础上，探索了有机小分子催化剂对不饱和羰基化合物δ位的官能团化及串联反应，同时在金属镍及铜催化的分子内关环反应中，可以得到一系列有机含氮杂环化合物，并应用于天然产物及药物分子骨架的合成，为新型实用的反应方法学发展提供了一定的基础。