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

Laetitia Bailly; Emilie Petit; Mayaka Maeno; Norio Shibata; Oliver Trapp; Pascal Cardinael; Isabelle Chataigner; Dominique Cahard

doi:10.1002/chir.22552

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

Chirality. 2016 Feb;28(2):136-42. doi: 10.1002/chir.22552. Epub 2015 Dec 21.

Authors

Laetitia Bailly¹, Emilie Petit¹, Mayaka Maeno^{1

2}, Norio Shibata², Oliver Trapp³, Pascal Cardinael⁴, Isabelle Chataigner¹, Dominique Cahard¹

Affiliations

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, Gokiso, Showa-ku, Nagoya, Japan.
³ Organisch-Chemisches Institut, Heidelberg, Germany.
⁴ Normandie Université, Laboratoire SMS EA 3233, Université de Rouen, Chromatography Unit, FR3038 INC3M, Mont Saint Aignan, France.

PMID: 26689286
DOI: 10.1002/chir.22552

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.

Keywords: DFT; chiral HPLC; enantiomerization; fluorine; sigmatropic rearrangement; sulfoxide; unified equation.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Chromatography, High Pressure Liquid / methods
Hydrocarbons, Fluorinated / chemistry*
Quantum Theory
Stereoisomerism
Sulfoxides / chemistry

Substances

Hydrocarbons, Fluorinated
Sulfoxides