Grignard类型反应合成3-胺基-2-吲哚酮类化合物  

Synthesis of 3-amino-2-oxindole derivatives through Grignard-type reaction

作　　者：贾义霞[1] 李翔 何俊青 JIA Yixia;LI Xiang;HE Junqing(College of Chemical Engineering,Zhejiang University of Technology,Hangzhou 310014,China)

机构地区：[1]浙江工业大学化学工程学院

出　　处：《浙江工业大学学报》2019年第5期479-484,共6页Journal of Zhejiang University of Technology

基　　金：国家自然科学基金资助项目(21772175,21522207)

摘　　要：以二价镍为催化剂、N-邻溴芳基α-亚胺酮酰胺为原料,在乙腈溶剂中,研究了其分子内溴苯对α-亚胺酮酰胺的■双键的亲核加成反应,成功实现了镍催化的Grignard类型亲核加成反应。系统优化了溶剂、温度、催化剂及锌粉还原剂的用量等影响反应的因素,并在确定的优化条件下对反应物的取代基进行考察,探索其适用范围,以中等到优异的产率得到一系列3-胺基-2-吲哚酮类化合物,为此类广泛存在于生物碱和生物活性分子中的重要骨架的合成提供了一种高效便捷的方法。Nickel(II)-catalyzed intramolecular Grignard-type nucleophilic addition of arylbromides to ketimines is developed with N-orthobromophenylα-imino ketoamides as starting material in acetonitrile solvent.The reaction conditions,including solvent,temperature,catalyst precursor and the amount of zinc powder,have been carefully optimized.The reactions under relatively mild conditions using 5%Ni(dppe)Br 2 as a catalyst led to a range of 3-amino-2-oxindoles with good to excellent yields,showing a good scope of the present reaction by varying the substituents of the substrates.The established reaction has provided an efficient access to synthesize such compounds,which are core substructures of a number of alkaloids and bioactive molecules.

关 键 词：镍 Grignard类型反应 分子内反应 酮亚胺 亲核加成 吲哚酮 

分 类 号：O62[理学—有机化学]