2,5-ANHYDRO-1-DEOXY-D-LYXITOL, 2,5-ANHYDRO-1-DEOXY-D-MANNITOL, AND 2,5-ANHYDRO-1-DEOXY-D-TALITOL. SYNTHESIS AND ENZYMIC STUDIES

Article abstract of DOI:10.1016/S0008-6215(00)80971-4

2,5-Anhydro-1-deoxy-D-mannitol (4), 2,5-anhydro-1-deoxy-D-talitol (8), and 2,5-anhydro-1-deoxy-D-lyxitol (12) were prepared by Raney-nickel desulfurization of 2,5-anhydro-D-mannose dihexyl dithioacetal (3), 2,5-anhydro-D-talose dihexyl dithioacetal (7), and 2,5-anhydro-D-lyxose diethyl dithioacetal (11), respectively, in 64percent yield based on starting thioacetal.Compounds 3 and 7 were prepared in 42percent yield, by the acid-catalyzed condensation of 2,5-anhydro-D-mannose and 2,5-anhydro-D-talose, respectively, with hexanethiol.Compound 11 was prepared in 66percent yield, by treatment of D-lyxose diethyl dithioacetal with p-toluenesulfonyl chloride-pyridine.Compounds 4,8,and 12 were examined as substrates and inhibitors for yeast hexokinase and bovine-liver fructokinase.Hexokinase and fructokinase phosphorylated 4 with K_m values of 25 and 1.94 mM, and V_max (4)/V_max (D-fructose) 0.007 and 0.13, respectively.Fructokinase was competitively inhibited by 8 and 12, with K_i values of 17 and 99 mM, respectively.