不对称[2+2+2]串联反应构建多手性含氮杂环化合物

本项目通过有机小分子催化的不对称[2+2+2]串联反应，研究以简单化学品为原料、温和的反应条件、高产率、高立体选择性构建具有连续多手性中心的含氮化合物，特别是全取代单环、并环、螺环及含有季碳手性中心的复杂含氮化合物高效的合成方法。主要研究包括：1）α-Aminoxylation/N-Michael/Aldol(或Mannich)不对称[2+2+2]串联反应；2）α-Hydroxyamination/O-Michael/Aldol(或Mannich)不对称[2+2+2]串联反应；3）基于去对称化的[2+2+2]不对称串联反应合成1,2-噁嗪手性砌块；4）不对称Michael/Michael/Aldol串联反应构建含有吲哚啉酮结构单元的螺[4.5]手性砌块；及5）基于去对称化的不对称[2+2+2]串联反应构建其它具有连续多手性中心的环状化合物。

This project aims to develop asymmetric [2+2+2] cascade reactions for the construction of nitrogen-containing heterocycles, especially those bearing contiguous stereocenters with bridged-cycles or spirocycles， from simple and readily available starting materials under mild conditions in high yields and stereoselectivities. The research includs five parts and they are, 1)the study of asymmetric α-aminoxylation/N-Michael/Aldol (or Mannich) [2+2+2] cascade reaction; 2) the study of asymmetric α-hydroxyamination/O-Michael/Aldol (or Mannich) [2+2+2] cascade reaction; 3)the study of asymmetric synthesis of chiral 1,2-oxazine building blocks via [2+2+2] cascade reaction involved desymmetric protocal ; 4)the study of asymmetric synthesis of indolinone-containing spiro-[4.5] compounds via Michael/Michael/Aldol cascade reaction; and 5) research and development of asymmetric construction of other cyclic compounds bearing contiguous stereocenters via [2+2+2] cascade reaction based on desymmetric strategy.The significance of this project lies in that the above-mentioned targets are of great synthetic value, while current methods for their preparation need to be improved.