【作者】 刘宇；

【导师】 段海峰；

【作者基本信息】 吉林大学 ， 有机化学， 2018， 硕士

【摘要】 本论文基于氨基酸骨架合成了两类相转移催化剂和部分文献中已知的催化剂,并对氨基砜与硝基甲苯的不对称nitro-Mannich反应和靛红酮亚胺与硝基甲烷的不对称nitro-Mannich反应进行了研究。本论文分为以下三部分:1.以廉价的L-叔亮氨酸为原料合成了两类相转移催化剂。一类是L-叔亮氨酸衍生的双氢键相转移催化剂,另一类是L-叔亮氨酸衍生的多氢键相转移催化剂。2.将已合成的L-叔亮氨酸衍生的两类相转移催化剂分别应用于氨基砜与硝基甲苯的不对称nitro-Mannich反应中,其中L-叔亮氨酸衍生的双氢键相转移催化剂催化该反应得到产物收率高达97%,ee高达99%,dr高达99:1。L-叔亮氨酸衍生的多氢键相转移催化剂催化该反应得到产物收率高达99%,ee高达98%,dr高达99:1。控制实验证明了氢键作用和季铵盐阳离子的协同催化对反应活性和立体选择性有重要影响。3.将已合成的L-叔亮氨酸衍生的相转移催化剂应用于靛红酮亚胺与硝基甲烷的不对称nitro-Mannich反应中,并对反应进行了初步的探索,在对反应条件优化的过程中发现,尽管反应活性良好,但产物的对映选择性较差,ee最高仅为49%。更多还原

【Abstract】 Two types of phase-transfer catalysts based on amino acid skeletons and some known catalysts were synthesized in this thesis.These phase-thansfer catalysts were applied to the asymmetric nitro-Mannich reaction of amino sulfone with aromatic nitroalkanes and asymmetric nitro-Mannich reaction of isatin-derived ketinines with nitromethane.This thesis was divided into the following three parts.1.We synthesized two types of phase transfer catalysts based on inexpensive L-tert-leucine.One was L-tert-leucine-derived double hydrogen bond phase-transfer catalysts,the other was L-tert-leucine-derived multi-hydrogen bond phase-transfer catalysts.2.We applied these two types of L-tert-leucine-derived phase-transfer catalysts to the asymmetric nitro-Mannich reaction of amino sulfone with aromatic nitroalkanes and got the corresponding products up to 97% yield,99% ee and 99:1 dr when the reaction was catalyzed by L-tert-leucine-derived double hydrogen bond phase-transfer catalysts.We obtained up to 99% yield,98% ee and 99:1 dr of products when the reaction was catalyzed by the L-tert-leucine-derived multi-hydrogen bond phase-transfer catalysts.At the same time,control experiments proved that the hydrogen bond and the quaternary ammonium had an important influence on the reactivity and stereoselectivity.3.We applied the L-tert-leucine-derived phase-transfer catalysts to the asymmetric nitro-Mannich reaction between isatin-derived ketimines and nitromethane.After conditions screening,the products showed good reactivity but the enantioselectivity was poor(49% ee).更多还原