β-ELIMINATION IN ALDONOLACTONES. SYNTHESIS OF 2-DEOXY-D-lyxo-HEXOSE AND 2-DEOXY-d-arabino-HEXOSE

Article abstract of DOI:10.1016/S0008-6215(00)83660-5

Benzoylation of D-glycero-L-manno-heptono-1,4-lactone (1) with benzoyl chloride and pyridine for 2 h afforded crystalline penta-O-benzoyl-D-glycero-L-manno-heptono-1,4-lactone (2), but a large excess of reagent during 8 h also led to 2,5,6,7-tetra-O-benzoyl-3-deoxy-D-lyxo-hept-2-enono-1,4-lactone (3).Catalytic hydrogenation of 3 was stereoselective and gave 2,5,6,7-tetra-O-benzoyl-3-deoxy-D-galacto-heptono-1,4-lactone (4).Debenzoylation of 4 followed by oxidative decarboxylation with ceric sulfate in aqueous sulfuric acid gave 2-deoxy-D-lyxo-hexose (5).Application of the same reaction to 3-deoxy-D-gluco-heptono-1,4-lactone afforded 2-deoxy-D-arabino-hexose (6).