Two-bond 13C-13C spin-coupling constants in carbohydrates: effect of structure on coupling magnitude and sign

An empirical projection method is described to predict the magnitudes and signs of two-bond 13C-13C spin-coupling constants (2JCC) in aldopyranosyl rings. The method has been applied primarily to the interpretation of 2JCCC values, although the behavior of 2JCOC has also been examined in light of the new approach, producing results which may prove useful in the conformational analysis of O-glycosidic linkages in oligosaccharides. High-level ab initio calculations of 2JCC values in model compounds were found to be in agreement with the predictions.