Synthesis and chiral recognition ability of O-phenyl ethylphosphonothioic acid with a conformationally flexible phenoxy group for CH/π interaction
Synthesis and chiral recognition ability of O-phenyl ethylphosphonothioic acid with a conformationally flexible phenoxy group for CH/π interaction
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DOI：
10.1016/j.tetasy.2006.03.009
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发表时间：
2006-03-20
影响因子：
--
通讯作者：
Saigo, Kazuhiko
中科院分区：
文献类型：
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作者：
Kobayashi, Yuka;Maeda, Jin;Saigo, Kazuhiko
以市售硫代磷酸酯为原料，经四步反应制得外消旋体1，经对映体拆分，得到对映体纯的O-苯基乙基硫代膦酸1。发现对映体纯1在非对映体盐形成过程中对各种1-芳基乙胺衍生物表现出优异的手性识别能力。特别地，对映体纯1能够识别o-和m-取代的1-芳基乙胺衍生物的手性，其手性通常难以通过常规拆分剂建立。X-射线衍射分析表明，对映体纯1中苯氧基的构象在非对映体盐晶体中发生了变化，对映体纯1的优良手性识别能力是由于苯氧基苯基的CH/π相互作用。(c)2006爱思唯尔有限公司版权所有。
Enantiopure O-phenyl ethylphosphonothioic acid 1 was easily obtained by the enantioseparation of racemic 1, which was prepared from commercially available phosphorothioic trichloride in four steps. Enantiopure 1 was found to show an excellent chiral recognition ability for various 1-arylethylamine derivatives during the diastereomeric salt formation. In particular, enantiopure 1 was able to recognize the chirality of o- and m-substituted 1-arylethylamine derivatives, of which the chirality is generally difficult to establish by conventional resolving agents. X-ray crystallographic analyses of the less-soluble diastereomeric salts revealed that the conformation of the phenoxy group in enantiopure 1 could change in the diastercomeric salt crystals and that the excellent chiral recognition ability of enantiopure 1 resulted from the effective CH/pi interaction of the phenoxy phenyl group. (c) 2006 Elsevier Ltd. All rights reserved.