Herein we report our investigation on the oxidation of solid-support-bound amino alcohols to their corresponding aldehydes. These aldehydes were converted into diastereomerically pure (>10:1) 2,4-cis-2-aminoalkyl-3-sulfonyl-1,3-oxazolidines using optically pure 1,2-amino alcohols. The relative configuration was determined using the nuclear Overhauser effect (NOE). The synthesized oxazolidines, which were obtained in high purities, represent a new, diverse scaffold for the solid-phase synthesis of libraries directed toward a pharmacological target.