新型手性胺双功能催化剂的设计、合成及其在不对称催化反应中的应用研究

项目名称： 新型手性胺双功能催化剂的设计、合成及其在不对称催化反应中的应用研究

项目编号： No.21302101

项目类型： 青年科学基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 徐大振

作者单位： 南开大学

项目金额： 25万元

中文摘要： 在本申请中，我们共设计了三种类型的新型双功能催化剂。首先，在我们原有较优催化剂的基础上引入了硫脲，合成了"手性胺-硫脲-吡啶"催化剂，通过形成氢键进一步提高催化剂对底物活化的能力；其次，我们将手性伯胺和磷酸结合在同一分子中，形成一类新型的、具有六元环状和七元环状结构的"手性伯胺-环状磷酸"双功能催化剂，通过两部分基团共同对底物进行活化，来拓展催化反应的类型、提高立体选择性；第三，我们将具有相转移作用的冠醚引入到手性胺催化剂中，得到"手性胺-冠醚"催化剂，利用冠醚部分的相转移功能及其与底物形成一定氢键的能力，达到对底物进行活化和稳定过渡态的作用。这些新型的双功能催化剂主要用于不对称C-C键的形成反应及相关的串联反应中，并对催化剂的双活化机理进行探讨,旨在扩展双功能有机催化剂在不对称合成中的应用，为天然产物、手性药物、农药及其它光学活性中间体的合成提供新方法。

中文关键词： 双功能催化剂；再利用；多组分反应；离子液体；绿色化学

英文摘要： In this application, we designed three kinds of novel chiral bifunctional organocatalysts. Firstly, we introduce thiourea group into the organocatalysts which have been synthesized before. The "chiral amine-thiourea-pyridine" catalysts are obtained which will promote the formation of hydrogen-bonding to activate substrates more effectively. Next, we combine chiral primary amine and phosphate into one small organic molecule. A new kind of "chiral primary amine-cyclic phosphate" catalysts with six member and seven member ring structure are obtained. These bifunctional organocatalysts will be applied more kinds of reactions, high enantioselectivity will be obtained through strong activation of the substrates by both of primary amine and br?nsted acid. Thirdly, we introduce crown ethers, which are often employed as effective phase-transfer catalysts, into the chiral amine organocatalysts. New bifunctional organocatalysts "chiral amine-crown ethers" are obtained. The crown ethers group in the catalyst will assist the chiral amine to activate substrates and stabilize transition state through efficient hydrogen-bonding interactions. These new bifunctional organocatalysts will be evaluated in asymmetric C-C bond formation reactions and relate domino reactions, and the dual activation model for the transition state will

英文关键词： bifunctional catalysis；recycling；multi-component reactions；ionic liquid；green chemistry