氧鎓离子介导的4-取代螺异恶唑啉的合成
Oxonium Ion Mediated Synthesis of 4-Substituted Spiro-Isoxazolines.
作者信息
McClendon Eric, Omollo Ann O, Valente Edward J, Hamme Ashton T
机构信息
Department of Chemistry, College of Science, Engineering and Technology, Jackson State University, Jackson, MS 39217 USA.
出版信息
Tetrahedron Lett. 2009 Feb 4;50(5):533-535. doi: 10.1016/j.tetlet.2008.11.053.
Abstract
The stereoselective synthesis of 4-bromo-spiro-isoxazolines was achieved in one step through the bromination of various isoxazoles that contain a pendant alcohol or carboxylic acid functional group. Isoxazole bromination leads to a bromonium ion intermediate which opens either by neighboring oxygen lone pair electrons or by intramolecular nucleophilic attack. Single X-ray crystal data provides evidence that the two contiguous stereocenters of the spiro-isoxazoline are formed by the anti intramolecular attack of the nucleophile relative to bromine since there is an anti stereochemical relationship between the spirocyclic ring oxygen and the bromine atom.
摘要
通过对各种含有侧链醇或羧酸官能团的异恶唑进行溴化反应，一步实现了4-溴代螺环异恶唑啉的立体选择性合成。异恶唑的溴化反应会生成一个溴鎓离子中间体，该中间体可通过邻近的氧孤对电子或分子内亲核攻击而开环。单晶X射线晶体数据表明，螺环异恶唑啉的两个相邻立体中心是由亲核试剂相对于溴的反式分子内攻击形成的，因为螺环中的环氧化合物与溴原子之间存在反式立体化学关系。
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