This work describes an extensive conformational analysis of Garner's aldehyde and its α-methylated homologue—two important chiral building blocks that are widely used in organic synthesis. A combination of density-functional theory and NMR spectroscopy confirmed the existence of a dynamic equilibrium between two possible conformers of the carbamate group in these compounds. The calculated properties such as conformer populations and rotational barriers around the (C
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O)–N bond are in good agreement with the experimental values. Finally, the dipole moments of the molecules appear to be a decisive factor in the stabilization of the conformers in solution.