Enantiomerization of Allylic Trifluoromethyl Sulfoxides Studied by HPLC Analysis and DFT Calculations
Enantiomerization of Allylic Trifluoromethyl Sulfoxides Studied by HPLC Analysis and DFT Calculations
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通过 HPLC 分析和 DFT 计算研究烯丙基三氟甲基亚砜的对映异构化
DOI：
10.1002/chir.22552
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发表时间：
2016
期刊：
影响因子：
2
通讯作者：
Dominique Cahard
中科院分区：
文献类型：
--
作者：
Laetitia Bailly;Emilie Petit;Mayaka Maeno;Norio Shibata;Oliver Trapp;Pascal Cardinael;Isabelle Chataigner;Dominique Cahard
在室温下，烯丙基三氟甲基亚砜通过相应的烯丙基三氟甲磺酸盐通过[2，3]-S型重排自发发生对映异构化反应。动态对映体选择性高效液相色谱分析揭示了在5~53 °C温度范围内，从色谱拆分到峰合并的立体动力学，测定了对映异构化速率常数和活化参数，并与密度泛函理论计算进行了比较。©2015 Wiley期刊，Inc.
Enantiomerization of allylic trifluoromethyl sulfoxides occurs spontaneously at room temperature through the corresponding allylic trifluoromethanesulfenates via a [2,3]‐sigmatropic rearrangement. Dynamic enantioselective high‐performance liquid chromatography (HPLC) analysis revealed the stereodynamics of these sulfoxides ranging from chromatographic resolution to peak coalescence at temperatures between 5 and 53 °C. The rate constant of enantiomerization and activation parameters were determined and compared with Density Functional Theory (DFT) calculations.Chirality 28:136–142, 2016. © 2015 Wiley Periodicals, Inc.