Enantiomerization of Allylic Trifluoromethyl Sulfoxides Studied by HPLC Analysis and DFT Calculations

Laëtitia Bailly (1) , Emilie Petit (1) , Mayaka Maeno (2) , Norio Shibata (2) , Oliver Trapp (3) , Pascal Cardinaël (4) , Isabelle Chataigner (1) , Dominique Cahard (1)

1 COBRA - Chimie Organique et Bioorganique : Réactivité et Analyse
2 Department of Frontier Materials, Department of Nanopharmaceutical Science
3 Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg,
4 SMS - Sciences et Méthodes Séparatives

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.

Domains: Chemical Sciences; Chemical Sciences; Analytical chemistry; Chemical Sciences; Organic chemistry

Laëtitia Bailly, Emilie Petit, Mayaka Maeno, Norio Shibata, Oliver Trapp, et al.. Enantiomerization of Allylic Trifluoromethyl Sulfoxides Studied by HPLC Analysis and DFT Calculations. Chirality, 2016, 28 (2), pp.136-142. ⟨10.1002/chir.22552⟩. ⟨hal-01928560⟩