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Enantiomerization of Allylic Trifluoromethyl Sulfoxides Studied by HPLC Analysis and DFT Calculations |
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| Authors: | Laetitia Bailly Emilie Petit Mayaka Maeno Norio Shibata Oliver Trapp Pascal Cardinael Isabelle Chataigner Dominique Cahard |
| Affiliation: | 1. UMR 6014 CNRS C.O.B.R.A., FR3038 INC3M, CNRS, Université de Rouen & INSA de Rouen, Mont Saint Aignan, France;2. Department of Nanopharmaceutical Science, Graduate School of Engineering, Nagoya Institute of Technology, Nagoya, Japan;3. Organisch‐Chemisches Institut, Heidelberg, Germany;4. Normandie Université, Laboratoire SMS EA 3233, Université de Rouen, Mont Saint Aignan, France |
| Abstract: | 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. |
| Keywords: | enantiomerization sulfoxide fluorine sigmatropic rearrangement chiral HPLC DFT unified equation |