Ab initio calculations, within the framework of density functional theory, were carried out on cyclohexane, 1,3-dioxane, 1,3-dithiane, 1,3-oxathiane, and 1,3-diazane. The one-bond C-13-H-1 NMR coupling constants were estimated according to the recently proposed theory by Malkin, Malkina, and Salahub. [Malkin, V. G.; Malkina, O. L.; Salahub, D. R. Chem. Phys. Lett. 1994, 221, 91]. No correlation between one-bond C-13-H-1 spin-spin coupling constants and the corresponding C-H bond distances was found. The direction of the Perlin effect, defined as the difference between the axial minus the equatorial one-bond C-H coupling constants, is correctly predicted by this methodology for all cases with the exception of one methylene group in 1,3-oxathiane. Thus, in general, the methodology is capable of reproducing subtle properties that are driven by. stereoelectronic interactions.