The C-3 deoxygenation of CDP-6-deoxy-l-threo-d-glycero-4-hexulose is the key step in the biosynthesis of ascarylose which is a 3, 6-dideoxy sugar found in the lipopolysaccharide of Yersinia pseudotuberculosis. This transformation, achieved by the catalysis of CDP-6-deoxy- l-threo-d-glycero-4-hexulose-3-dehydrase (E1) and CDP-6-deoxy-l-threo-d-glycero-4- hexulose-3-dehydrase reductase (E3), is initiated by a reversible dehydration followed by ...