立体选择性环化反应研究：吡唑啉及其衍生物的新合成策略

项目名称： 立体选择性环化反应研究：吡唑啉及其衍生物的新合成策略

项目编号： No.21272087

项目类型： 面上项目

立项/批准年度： 2013

项目学科： 数理科学和化学

项目作者： 陈加荣

作者单位： 华中师范大学

项目金额： 80万元

中文摘要： 吡唑啉是一类重要的五元氮杂环化合物。这类杂环化合物具有广谱的生物活性。但是，这类化合物的立体选择性合成仍然具有一定的挑战性。本项目拟将基于α-卤代腙试剂发展多官能化吡唑啉衍生物的新合成策略，重点研究：1）卤代腙与硫叶立德的极性反转/[4+1]环化反应；2）卤代腙与氮叶立德的极性反转/[4+1]环化反应；3）卤代腙与碳酸烯丙酯的极性反转/[4+1]环化反应；4）卤代腙与氧化吲哚的极性反转/[4+1]环化反应；5）卤代腙与取代吲哚的极性反转/[4+2]环化反应；6）天然产物Alline和CPC-1类似物的全合成；7）机理研究和反应设计。重点解决形成氮杂二烯的条件和环加成反应条件的兼容性以及如何提高反应的立体选择性。通过这些研究，力图为结构多样、多官能化的吡唑啉衍生物的高效、高选择性构建提供新的方法。本项目的实施为特定功能分子和结构体系的高效、经济与绿色合成提供一定的理论指导和实验依据

中文关键词： 不对称催化；杂环；吡唑啉；含氮杂环；环加成

英文摘要： The pyrazolines are an important class of five-membered aza-heterocycles that exhibit a wide range of biological activities. However, the enantioselective synthesis of these heterocycles is still a desirable but challenging task for organic chemists. In this project, we will focus on developing new strategies for the enantioselective synthesis of pyrazoline derivatives, mainly including: 1) umpolung/[4+1] annulation reaction between halogenated hydrazones and sulfur ylides; 2) umpolung/[4+1] annulation reaction between halogenated hydrazones and ammonium ylides; 3) umpolung/[4+1] annulation reaction between halogenated hydrazones and allylic carbonates; 4) umpolung/[4+1] annulation reaction between halogenated hydrazones and 3-substituted oxindoles; 5) umpolung/[4+2] annulation reaction between halogenated hydrazones and substituted indoles; 6) total synthesis of natural products Alline and CPC-1 analogues. During the course of these studies, we will also extensively explore the possible mechanism of the above reactions to design other novel reactions.We will investigate the compatibility between the conditions for the generation of reactive azoalkene and the following asymmetric cycloaddition. By doing so, we will try to develop a series of new methods for the highly efficient and enantioselective construction

英文关键词： asymmetric catalysis；heterocycles；pyrazolines；nitrogen heterocycles；cycloaddition