有机催化环状磺酰基亚胺的不对称Mannich反应

发布时间：2018-04-11 03:15

本文选题：Mannich反应 + 不对称催化　；参考：《河南大学》2016年硕士论文

【摘要】：氨基磺酸酯是合成许多重要有机化合物如天然产物、药物活性分子等的重要中间体,在有机合成中具有重要作用。我们研究了伯胺催化的苯并环状氮磺酰亚胺与甲基烷基酮的不对称直接Mannich反应,高对映选择性和区域选择性的合成了一系列手性氨基磺酸酯类化合物,取得了高达99%的收率和97%的对映选择性。值得注意的是,可能是由于空间位阻的原因,当我们使用非对称的甲基烷基酮作为亲核试剂时,反应位点在含有较少取代基的位置。我们也研究了伯胺和三氟乙酸共催化的芳基甲基酮与苯并环状氮磺酰亚胺的不对称Mannich反应,一系列含有各种带有不同电子效应以及立体效应的取代基的芳基甲基酮都能很好地适用于此高对映选择性Mannich反应,并取得非常高的收率和对映选择性(99%的产率和98%的ee值)。Knoevenagel反应作为构建碳碳键的重要方法,曾得到广大化学工作者的深入研究,并被广泛应用于化学工业生产中。我们用新颖的两性阴阳离子型季铵盐催化剂,实现了芳基醛与丙二腈的Knoevenagel缩合反应,并取得了高达97%的收率。
[Abstract]:Aminosulfonic acid esters are important intermediates in the synthesis of many important organic compounds such as natural products and drug active molecules, which play an important role in organic synthesis.A series of chiral aminosulfonic acid esters were synthesized by asymmetric direct Mannich reaction of benzocyclic azosulfoimide with methyl alkyl ketones catalyzed by primary amines with high enantioselectivity and regioselectivity.Up to 99% yield and 97% enantioselectivity were obtained.It is worth noting that it may be due to the steric hindrance that when asymmetric methyl alkyl ketones are used as nucleophilic reagents the reaction sites are located with less substituents.We have also studied the asymmetric Mannich reaction of aromatic methyl ketones with benzocyclic azosulfonimide catalyzed by primary amine and trifluoroacetic acid.A series of aryl methyl ketones containing various substituents with different electron effects and stereoscopic effects are well suited for this highly enantioselective Mannich reaction.A very high yield, enantioselectivity of 99% yield and 98% ee value of Knoevenagel reaction were obtained as an important method for the construction of carbon-carbon bond, which has been studied by many chemical workers and widely used in chemical industry.The Knoevenagel condensation of aryl aldehydes with malonitrile was realized with a novel amphoteric anion quaternary ammonium salt catalyst and the yield was as high as 97%.
【学位授予单位】：河南大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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