2-O-a-D-Galactopyranosyl-L-rhamnopyranose, which is structurally related to Me urobioside, was prepd. by glycosidation of benzyl 3,4-di-O-benzoyl-a-L-rhamnopyranoside with Me 2,3,4,6-tetra-O-benzyl-1-thio-b-D-galactopyranoside (Me triflate, Et2O, mol. sieves) followed by deprotection (MeONa-MeOH; H2, Pd/C). Also prepd. was 2-O-a-D-galactopyranosyl-D-mannopyranose via Ag triflate-promoted glycosidation of benzyl 3,4,6-tri-O-benzyl-a-D-mannopyranoside with 2,3,4,6-tetra-O-benzyl-a-D-galactopyranosyl chloride followed by catalytic hydrogenolysis. [on SciFinder (R)]