An ingenious method for the determination of the relative and absolute configurations of compounds containing aryl-glycerol fragments by 1 H NMR spectroscopy.

A concise method was established to determine the relative and absolute configurations of aryl-glycerols that depend on the chemical shift differences (Δ δ ) of the diastereotopic methylene protons (H-3) by 1 H NMR spectroscopy. When using DMSO- d 6 as the preferred solvent, the threo configuration corresponded to a larger Δ δ H3a-H3b value (>0.15 ppm), whereas the erythro configuration (<0.07 ppm) corresponded to a smaller value. Furthermore, the absolute configurations were determined with the aid of a simple acylation reaction through camphanoyl chloride. In the threo enantiomers, the Δ δ value of the 1 R ,2 R configuration was <0.15 ppm, and that of the 1 S ,2 S configuration was >0.20 ppm. In the erythro enantiomers, the Δ δ value of 1 R ,2 S was >0.09 ppm, and that of 1 S ,2 R was <0.05 ppm. Remarkably, this empirical rule is invalid in CDCl 3 . In addition, this method was also verified by a quantum 1 H NMR calculation.