Deoxygenation of thiazolylketose acetates using SmI 2 -(CH 2 OH) 2 or TMSOTf-Et 3 SiH affords thiazolyl C-glycosides with opposite α/β ratios. Examination of the thiazolyl α- and β-C-ribofuranoside pair by NOE experiments reveals that the earlier configuration assigned to one of these isomers has to be revised. Having prepared authentic anomeric α- and β-ribofuranose aldehydes from the corresponding thiazolyl C-glycosides by cleavage of the thiazole ring, each aldehyde was transformed into (1->6)-C-disaccharides via Wittig olefination with a galactose 6-phosphorane.