title: Enantiomerization of Allylic Trifluoromethyl Sulfoxides Studied by HPLC Analysis and DFT Calculations.
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.
authors.affiliation: UMR 6014 CNRS C.O.B.R.A., FR3038 INC3M, CNRS, Université de Rouen & INSA de Rouen, Mont Saint Aignan, France.
authors.forename: Laetitia
authors.initials: L
authors.lastname: Bailly
authors.affiliation: UMR 6014 CNRS C.O.B.R.A., FR3038 INC3M, CNRS, Université de Rouen & INSA de Rouen, Mont Saint Aignan, France.
authors.forename: Emilie
authors.initials: E
authors.lastname: Petit
authors.affiliation: UMR 6014 CNRS C.O.B.R.A., FR3038 INC3M, CNRS, Université de Rouen & INSA de Rouen, Mont Saint Aignan, France.|Department of Nanopharmaceutical Science, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya, Japan.
authors.forename: Mayaka
authors.initials: M
authors.lastname: Maeno
authors.affiliation: Department of Nanopharmaceutical Science, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya, Japan.
authors.forename: Norio
authors.initials: N
authors.lastname: Shibata
authors.affiliation: Organisch-Chemisches Institut, Heidelberg, Germany.
authors.forename: Oliver
authors.initials: O
authors.lastname: Trapp
authors.affiliation: Normandie Université, Laboratoire SMS EA 3233, Université de Rouen, Chromatography Unit, FR3038 INC3M, Mont Saint Aignan, France.
authors.forename: Pascal
authors.initials: P
authors.lastname: Cardinael
authors.affiliation: UMR 6014 CNRS C.O.B.R.A., FR3038 INC3M, CNRS, Université de Rouen & INSA de Rouen, Mont Saint Aignan, France.
authors.forename: Isabelle
authors.initials: I
authors.lastname: Chataigner
authors.affiliation: UMR 6014 CNRS C.O.B.R.A., FR3038 INC3M, CNRS, Université de Rouen & INSA de Rouen, Mont Saint Aignan, France.
authors.forename: Dominique
authors.initials: D
authors.lastname: Cahard
mesh_terms: D002851:Chromatography, High Pressure Liquid / Q000379:methods; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism; D013454:Sulfoxides / Q000737:chemistry
chemical_list: D006845:Hydrocarbons, Fluorinated; D013454:Sulfoxides
keywords: DFT; chiral HPLC; enantiomerization; fluorine; sigmatropic rearrangement; sulfoxide; unified equation