Geometry optimizations at the B3LYP level of density functional theory (DFT) are reported for methyl 4-O-acetyl-3-azido- and 3-azido-4-O-methylsulfonyl-2,3,6-trideoxy-alpha,beta-D-threo- and -beta-D-erythro-hex-5-enopyranosides. The most stable conformers for each compound are presented, along with the corresponding enthalpies and Gibbs free energies. The influence of the exocyclic double bond on the chair conformation is discussed. Conformations of the 1-OMe, 3-N-3, and 4-OAc groups were examined, and delocalization in the OAc and N-3 groups was demonstrated. The contributions of particular conformers to the total number of structures found for each hex-5-enopyranoside were calculated. The theoretical results are compared with assignments based on H-1 NMR studies.