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

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 (Δδ 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 α- and β-position to sulfur were successfully used for distinguishing between the diastereoisomeric sulfoxides.

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