Asymmetric Synthesis of Dihydroindanes by Convergent Alkoxide-Directed Metallacycle-Mediated Bond Formation
作者:Stephen N. Greszler、Holly A. Reichard、Glenn C. Micalizio
DOI:10.1021/ja2105043
日期:2012.2.8
A convergent synthesis of highly substituted and stereodefined dihydroindanes is described from alkoxide-directed Ti-mediated cross-coupling of internal alkynes with substituted 4-hydroxy-1,6-enynes (substrates that derive from 2-directional functionalization of readily available epoxy alcohol derivatives). In addition to describing a new and highly stereoselective approach to bimolecular [2 + 2 +
内部炔烃与取代的 4-羟基-1,6-烯炔(源自易于获得的环氧醇衍生物的 2 向功能化的底物)的醇盐导向的 Ti 介导的交叉偶联描述了高度取代和立体定义的二氢茚的收敛合成)。除了描述一种新的和高度立体选择性的双分子 [2 + 2 + 2] 环化方法,该方法可提供该化学反应领域其他方法无法提供的产品,还提供了支持通过区域选择性炔-炔偶联的方法进行环化的证据,其次是以金属为中心的 [4 + 2] 而不是逐步的烯烃插入和还原消除。总体而言,该反应以精细的立体化学控制进行,并定义了一个方便的、收敛的、