Regioselective benzoylations of N-(2,2-diethoxycarbonylvinyl)-beta-L-rhamnopyranosylamine (1) yielded 2,3-di-O- (3), 3,4-di-O- (4), and 3-O-benzoyl-N-(2,2-diethoxycarbonylvinyl)-beta-L-rhamnopyranosylamine (5) together with the tri-O-benzoylated derivative 2. Syntheses of 2,3,4-tri-O-benzoyl-beta-L-rhamno- (7) and -beta-L-fuco-pyranosyl isothiocyanate (13) from 2 and L-fucopyranosylamine, respectively, are described. N-Phenacyl-N'-(2,3,4-tri-O-benzoyl-beta-L-rhamno- (8) and -beta-L-fuco-pyranosylthiourea (14) were prepared from 7 and 13, respectively, by reaction with phenacylamine. Conformational properties and MS data of the prepared compounds are discuss