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Enantiomerization of Allylic Trifluoromethyl Sulfoxides Studied by HPLC Analysis and DFT Calculations
Author(s) -
Bailly Laetitia,
Petit Emilie,
Maeno Mayaka,
Shibata Norio,
Trapp Oliver,
Cardinael Pascal,
Chataigner Isabelle,
Cahard Dominique
Publication year - 2016
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.22552
Subject(s) - chemistry , allylic rearrangement , trifluoromethyl , high performance liquid chromatography , coalescence (physics) , enantioselective synthesis , density functional theory , chromatography , medicinal chemistry , computational chemistry , organic chemistry , catalysis , alkyl , physics , astrobiology
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.