as a function of q 2 in 1 c -5 c (Figure , Supporting Information). Similar behavior is expected from rotation of the C1-O1 bond, but only one C1-O1 rotamer (f) was considered in this work, being the most populated based on stereoelectronic factors (exo-anomeric effect). a-Anomers 1 and 3 give slightly smaller calculated 1 J C1,C2 values than b-anomers 2 and 4, consistent with the behavior of experimental 1 J C1,C2 values in the anomers of methyl D-glucopyranoside and methyl D-galactopyranoside in aqueous solution (Table ). The plots in Figure show that (Figure , Supporting Information) shows that r C5,C6 is longer in the tg rotamer than in the gg and gt rotamers, leading to the expectation that 1 J C5,C6 should be smaller in the former (less scharacter). However, the opposite behavior is observed. Thus, structural factors in addition to C5-C6 bond length appear responsible for the behavior shown in Figure .