Two five-membered cyclic nitrones derived from hexoses, a newly synthesized D-allo-configured nitrone and an already known D-talo-configured nitrone, have been examined in 1,3-dipolar cycloaddition reactions with vinyl acetate, allyl benzoate, methyl acrylate, acrylonitrile, and vinylene carbonate. The reactions of the D-allo-configured nitrone proceeded preferentially through the expected exo-anti transition state, but all the cycloadditions of the D-talo-configured nitrone surprisingly showed high exo-syn selectivity. This reversal of stereoselectivity has been explained by 3D analysis of the preferred conformations of the nitrones, obtained from X-ray data. The structures were further inspected using CONFLEX, PM5, and DFT calculations. All these methods revealed that the dioxolane substituents attached to C-5 of both nitrones had opposite spatial locations.