Key Laboratory of Green Chemistry &Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, P. R. China.
Chemistry. 2021 Jun 25;27(36):9272-9275. doi: 10.1002/chem.202100829. Epub 2021 May 28.
A chiral N,N'-dioxide-nickel(II) complex-catalyzed asymmetric amination of 3-bromo-3-substituted oxindoles with anilines has been developed. A series of alkyl or aryl 3-amino-indolinones with quaternary stereocenters were obtained in high yields with excellent ee values in one step (up to 99 % yield, up to 96 % ee). The method provided a ready route to optically active intermediates of 3-amino-2-oxindole-based bioactive compounds. Moreover, a possible transition-state model is proposed so as to elucidate the origin of the chirality based on the X-ray crystal structure of the catalyst and the adduct.
已开发出一种手性 N,N'-二氧代镍（II）配合物催化的 3-溴-3-取代氧吲哚与苯胺的不对称胺化反应。通过一步反应，可以高收率和优异的对映选择性（高达 99%的产率，高达 96%的对映体过量值）获得一系列具有季立体中心的烷基或芳基 3-氨基-吲哚啉酮。该方法为基于 3-氨基-2-氧吲哚的生物活性化合物的手性中间体制备提供了一条简便途径。此外，基于催化剂和加合物的 X 射线晶体结构，提出了一个可能的过渡态模型，以阐明手性的起源。
