Department of Chemistry, University of Minnesota Twin Cities , Minneapolis, Minnesota 55455, United States.
J Am Chem Soc. 2018 Jan 31;140(4):1211-1214. doi: 10.1021/jacs.7b11299. Epub 2018 Jan 10.
This report describes the stereoselective synthesis of 3-azido-tetralins, -chromanes, and -tetrahydroquinolines via a tandem allylic azide rearrangement/Friedel-Crafts alkylation. Exposure of allylic azides with a pendant trichloroacetimidate to catalytic quantities of AgSbF proved optimal for this transformation. This cascade successfully differentiates the equilibrating azide isomers, providing products in excellent yield and selectivity (>25 examples, up to 94% yield and >25:1 dr). In many cases, the reactive isomer is only a trace fraction of the equilibrium mixture, keenly illustrating the dynamic nature of these systems. We demonstrate the utility of this process via a synthesis of hasubanan.
本报告描述了通过串联烯丙基叠氮重排/Friedel-Crafts 烷基化反应立体选择性合成 3-叠氮四氢萘、-色满和-四氢喹啉。暴露于带有三氯乙酰亚胺酯侧链的烯丙基叠氮化物与催化量的 AgSbF 证明是这种转化的最佳选择。这种级联反应成功地区分了平衡的叠氮异构体，以优异的收率和选择性（>25 个实例，收率高达 94%，dr 值>25:1）提供产物。在许多情况下，反应性异构体仅是平衡混合物中的微量部分，这清楚地说明了这些体系的动态性质。我们通过合成哈苏巴南证明了该过程的实用性。
