POTENTIAL BILE-ACID METABOLITES .23. SYNTHESES OF 3-GLUCOSIDES OF NONAMIDATED AND GLYCINE-AMIDATED AND TAURINE-AMIDATED BILE-ACIDS

The 3-glucosides of nonamidated lithocholic, chenodeoxycholic, ursodeo xycholic, deoxycholic, and cholic acids, and their double conjugate fo rms with glycine and taurine were synthesized. The key reactions used were 1) beta-D-glucosidation at C-3 by the Koenigs-Knorr condensation reaction of 3 alpha-hydroxylated bile acid methyl (or p-nitrophenyl) e sters with 1 omo-1-deoxy-2,3,4,6-tetra-O-acetyl-D-glucopyranose in the presence of cadmium carbonate in refluxing benzene; 2) indirect and d irect amidations at C-24 by the activated p-nitrophenyl ester and by t he diethylphosphorylcyanide methods, respectively, using glycinate est er and taurine as coupling agents; and 3) simultaneous alkaline hydrol ysis of the hydroxyl-protecting and ester groups in both the sugar and aglycone moieties.