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- Title
Circular Dichroism and TDDFT Investigation of Chiral Fluorinated Aryl Benzyl Sulfoxides.
- Authors
Berardozzi, Roberto; Guido, Ciro A.; Capozzi, Maria Annunziata M.; Cardellicchio, Cosimo; Di Bari, Lorenzo; Pescitelli, Gennaro
- Abstract
A series of ten chiral aryl benzyl sulfoxides with perfluorinated aryl or benzyl rings, obtained by enantioselective oxidation of sulfides, has been investigated by means of electronic circular dichroism (ECD) spectroscopy and time-dependent DFT (TDDFT) calculations. The (per)fluorination of the aromatic rings has a large impact on the conformer population, the molecular orbitals shape, and the character of electronic transitions. In this series, the transition responsible for the 'sulfoxide primary' CD band has a large charge transfer (CT) character, as demonstrated by the CT metric index ΓNTO. As a consequence, global DFT hybrids such as B3LYP are largely inaccurate in the prediction of excited states; nevertheless, a correct simulation of CD spectra may be achieved by using range-separated functionals such as CAM-B3LYP. The use of the empirical Mislow's rule for assigning the absolute configuration is strongly discouraged for this class of compounds.
- Subjects
CIRCULAR dichroism; TIME-dependent density functional theory; BENZYL compounds; SULFOXIDE derivatives; SPECTROMETRY; CHARGE transfer
- Publication
European Journal of Organic Chemistry, 2015, Vol 2015, Issue 25, p5554
- ISSN
1434-193X
- Publication type
Article
- DOI
10.1002/ejoc.201500648