The determination of sulfoxide configuration in six-membered rings using NMR specroscopy and DFT calculations

0360400 - ÚOCHB 2012 RIV GB eng J - Journal Article
Dračínský, Martin - Pohl, Radek - Slavětínská, Lenka - Janků, J. - Buděšínský, Miloš
The determination of sulfoxide configuration in six-membered rings using NMR specroscopy and DFT calculations.
Tetrahedron Asymmetry. Roč. 22, č. 3 (2011), s. 356-366. ISSN 0957-4166
R&D Projects: GA ČR GA203/09/1919
Institutional research plan: CEZ:AV0Z40550506
Keywords : NMR * calculation of NMR parameters * sulfoxides * configuration
Subject RIV: CC - Organic Chemistry
Impact factor: 2.652, year: 2011

Cyclic six-membered ring sulfoxides and sulfones were prepared by a stepwise in situ oxidation of the corresponding sulfides with meta-chloroperbenzoic acid in an NMR tube. The oxidation was followed by NMR spectra and the 1H and 13C NMR data were collected. The geometries of all of the compounds were optimized using the DFT B3LYP/6-31G** method and the 13C and 1H NMR chemical shifts were calculated for geometry-optimized structures with the DFT B3LYP/6-31++G** method. The calculated 13C NMR chemical shifts induced by oxidation (Dd values) are in very good agreement with the experimental data and can be used to determine the oxidation state of the sulfur atom (–S–, –SO–, –SO2–). The characteristic differences of the induced oxidation chemical shifts of carbon atoms at the a- and b-position to sulfur were successfully used for distinguishing between the diastereoisomeric sulfoxides.
Permanent Link: http://hdl.handle.net/11104/0197965