Chemical Development, Boehringer-Ingelheim Pharmaceuticals, Inc., 900 Ridgebury Road, Ridgefield, Connecticut 06877, United States.
Department of Chemistry, South University of Science and Technology of China , Shenzhen, 518000, P. R. China.
Org Lett. 2017 Jul 7;19(13):3338-3341. doi: 10.1021/acs.orglett.7b01054. Epub 2017 Jun 12.
The development of enantioselective carbon-carbon bond couplings catalyzed by nonprecious metals is highly desirable in terms of cost efficiency and sustainability. The first nickel-catalyzed enantioselective Mizoroki-Heck coupling is reported. This transformation is accomplished via mild reaction conditions, leveraging on QuinoxP* as a chiral ligand to afford oxindoles containing quaternary stereocenters. Good reactivity and selectivity are observed in the presence of various functional groups. Computational studies suggest that the oxidative addition assembles an atropisomeric intermediate responsible for the facial selectivity of the insertion step.
非贵金属催化的对映选择性碳-碳键偶联的发展在成本效益和可持续性方面具有很高的需求。本文首次报道了镍催化的对映选择性 Mizoroki-Heck 偶联反应。该转化通过温和的反应条件实现,利用 QuinoxP*作为手性配体,以提供含有季立体中心的吲哚酮。在存在各种官能团的情况下,观察到良好的反应活性和选择性。计算研究表明,氧化加成组装了一个手性中间体,负责插入步骤的面选择性。