【作者】 姚其波；

【导师】 陶京朝； 王兴旺；

【作者基本信息】 郑州大学 ， 有机化学， 2010， 硕士

【摘要】 本文首先对近年来氮杂-Baylis-Hillman反应的发展进行了综述,然后,我们对亚胺与丙烯酸甲酯的氮杂-Baylis-Hillman反应进行了研究,分别以非手性的亚磷酸酯和一系列3,3’-位具有较大位阻的联萘骨架的手性膦酸为催化剂对该反应进行了尝试,分别得到了外消旋的和手性的α-亚甲基β-胺基羰基类化合物：一.以非手性的亚磷酸酯为催化剂,对亚胺与丙烯酸甲酯的氮杂-Baylis-Hillman反应进行了研究,分别对该反应的溶剂、温度、浓度、催化剂、底物进行了筛选,以25-79%的产率得到了外消旋体,为手性膦酸催化的氮杂-Baylis-Hillman反应奠定了基础。以廉价易得的(R)-BINOL为原料,通过酚氧基保护、Suzuki或Kumada偶联、脱保护,然后在碱性条件下与POCl3反应、水解,合成了一系列3,3’-位具有较大位阻的联萘骨架的手性膦酸；分别用核磁共振氢谱、核磁共振碳谱、质谱,旋光对该系列膦酸进行了表征。三.以该系列3,3’-位具有较大位阻的联萘骨架的手性膦酸为催化剂尝试对不对称的氮杂-Baylis-Hillman反应进行了研究,分别对该反应体系的溶剂、手性膦酸类催化剂及底物进行了考察,最终,在室温条件下,以1,4-dioxane为溶剂、3,3’-位均为3,5-二甲基苯基取代基的手性膦酸18-DABCO为共催化剂催化的氮杂-Baylis-Hillman反应最高能以80%的产率、31%的对映选择性得到产物。更多还原

【Abstract】 In this thesis, firstly we viewed the development of aza-Bayllis-Hillman reaction in recent years, then, the aza-Bayllis-Hillman reactions catalyzed by achiral phosphite and chiral phosphoric acid with steric hindrance at 3,3’-position were studied, and the target compoundsα-methylene-β-aminocarbonyl derivatives in the form of racemates and chiral materials were obtained:1. The aza-Bayllis-Hillman reactions of imines and methyl acrylate catalyzed by achiral phosphite were studied. The reaction conditions, such as solvent, temperature, concentration, catalysts, and substrates were screened. The target aza-Bayllis-Hillman reaction products were obtained with 25-79% yield, which provided the racemates for the chiral phosphoric acid catalyzed aza-Bayllis-Hillman reactions.2. A series of chiral phosphoric acid with steric hindrance at 3,3’-position were synthesized via multistep transformations from cheap and readily available (R)-BINOL, including pretection of hydroxyl group, Suzuki or Kumada coupling reaction, depretection, reaction with POCl3 under alkaline condition, then hydrolysis. And these chiral phosphoric acids were characterized by 1H-NMR,13C-NMR, MS and [α]D20, respectively. 3. Subsequently, we applied these chiral phosphoric acids to the asymmetric aza-Bayllis-Hillman reactions of imines and methyl acrylate. And different solvents, br(?)nsted acids, substrates were investigated. As a result, the reaction with the solvent of 1,4-dioxane, catalyzed by catalysis 18 was finished with 80% yield and 31% enantioselectivity.更多还原