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Enantiomerization of Allylic Trifluoromethyl Sulfoxides Studied by HPLC Analysis and DFT Calculations
Laetitia Bailly1, Emilie Petit1, Mayaka Maeno1,2
1UMR 6014 CNRS C.O.B.R.A., FR3038 INC3M, CNRS, Université de Rouen & INSA 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.
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