Preliminary stereochemical investigation of the Atherton-Todd-type reaction between valine hydrospirophosphorane and phenols
Preliminary stereochemical investigation of the Atherton-Todd-type reaction between valine hydrospirophosphorane and phenols
复制标题
缬氨酸氢螺正膦与酚类 Atherton-Todd 型反应的初步立体化学研究
DOI：
10.1016/j.tetlet.2012.09.056
复制
发表时间：
2012-11-14
影响因子：
1.8
通讯作者：
Zhao, Yufen
中科院分区：
文献类型：
--
作者：
Cao, Shuxia;Guo, Yanchun;Zhao, Yufen
首次研究了由L-缬氨酸与酚类化合物合成五配位螺氢膦的Atherton-Todd型反应。立体定向合成了一系列新型苯氧基螺膦化合物，并通过P-31 NMR示踪实验和X-射线衍射分析初步探讨了其立体化学机理。该反应通过初始生成的氯代螺正膦中间体与保留的配置在磷，然后由亲核取代与苯酚的后部攻击，以产生苯氧基螺正膦与立体转化的磷手性中心进行。(C)2012爱思唯尔有限公司保留所有权利。
The Atherton-Todd-type reaction of pentacoordinate hydrospirophosphoranes synthesized from L-valine with phenols was first investigated. A series of new types of phenoxy spirophosphoranes were stereospecifically synthesized and a preliminary stereochemical mechanism was proposed by P-31 NMR tracing experiments and X-ray diffraction analysis. The reaction proceeded via the initial generation of chlorinated spirophosphorane intermediate with retention of the configuration at phosphorus, followed by the rear attack of nucleophilic substitution with phenols to produce phenoxy spirophosphoranes with stereoinversion of the phosphorus chiral center. (C) 2012 Elsevier Ltd. All rights reserved.