Three representative spirostanol saponins that have typical structure of the sugar moiety, diosgenyl 2,3-di-O-alpha-(L)-rhamnopyranosyl-beta-(D)-glucopyranoside, diosgenyl 2,4-di-O-alpha-(L)-rhamnopyranosyl- beta-(D)-glucopyranoside (dioscin), and diosgenyl 2,6di-O-alpha-(L)-rhamnopyranosyl-beta-(D)-glucopyranoside, were synthesized in a facile way. An approach to selectively mask the C-3-hydroxyl of diosgenyl 4,6-O-benzylidene beta-(D)-glucopyranoside was described. A procedure using cerium(IV) ammonium nitrate for selective removal of tert-butyldimethylsilyl group while retaining levulinyl group is afforded.