Department of Chemistry, University of Kansas , 1251 Wescoe Hall Drive, Lawrence, Kansas 66045, United States.
Leibniz-Institut für Katalyse e.V. an der Universität Rostock , Albert-Einstein Straße 29a, Rostock 18059, Germany.
Org Lett. 2016 Dec 16;18(24):6272-6275. doi: 10.1021/acs.orglett.6b03068. Epub 2016 Dec 2.
An efficient approach toward enantioenriched eight-membered heterocycles via the intramolecular formal substitution of bromocyclopropanes with oxygen-based nucleophiles has been developed. The reaction proceeds via a reactive cyclopropene intermediate, which undergoes a rapid 8-endo-trig cyclization affording cis-fused [6.1.0] bicyclic products exclusively. The quaternary chiral center in the cyclopropene governs the configuration of the other two stereocenters in the final product.
通过溴环丙烷与含氧亲核试剂的分子内形式取代，开发了一种高效的方法来制备对映体富集的八元杂环。该反应通过反应性环丙烯中间体进行，该中间体经历快速的 8-endo-trig 环化，仅得到顺式稠合[6.1.0]双环产物。环丙烯中的季碳原子控制最终产物中另外两个立体中心的构型。
