The properties of chiral spirochalcogenuranes acting as ligands in adducts with a chiral dirhodium tetracarboxylate complex is explored, and the individual adduct species are characterized by low-temperature NMR spectroscopy. Chiral recognition and the determination of enantiomeric composition of the chiral spirochalcogenuranes is easy by evaluating NMR signal dispersions both at low and at room- or slightly elevated temperatures. The uniformity in the signs of 1H dispersion effects and taking reference to the spiroselenurane with known absolute configuration [(S)-(-)-2] indicates that a convenient rule for the determination of absolute configuration in the spirochalcogenurane system can be established on the basis of 1H chemical shift dispersions.

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