Amiprilose hydrochloride is a carbohydrate-derived, novel anti-inflammatory with potential application in the treatment of rheumatoid arthritis. A spectroscopy-based approach was undertaken to assign both the relative and absolute configuration of its five chiral centers. The fully assigned I3C and 'H NMR spectra of amiprilose hydrochloride was used to establish the relative stereochemistry of four of its five chiral centers held rigid in its furanose ring system. Parallel synthesis of the enantiomer of amiprilose hydrochloride from L-glucose was followed by CD spectropolarimetry to establish that no inversion of chiral centers had occurred in the synthesis. The hydrobromide salt of amiprilose and its enantiomer were prepared and, together with amiprilose hydrochloride, were crystallized. X-ray crystallographic analysis resulted in the assignment of the absolute configuration of all five chiral centers. Amiprilose hydrochloride (4; Therafectin) i s a novel antiinflammatory d r u g derived synthetically from D-glucose, and is currently in advanced phase IYIII clinical trials. In preclinical studies, ami rilose hydrochloride has been shown to d e c t inflammation a n d to increase the killing activity of peritoneal-derived lymphocyte^.^.^ Additionally, the substance suppresses the appearance of Type I1 collagen-induced adjuvant arthritis i n rats4 This d r u g i s synthesized from D-glucose (1) by converting it t o a-D-l,2:5,6-di-O-isopropylidene glucofuranose (21, thus leaving only the 3-hydroxyl group unblocked. Following 3-0-alkylation with 1,NJV-