Oxaunomycin (3) and its regioisomer (6) were synthesized by employing regioselective glycosidations of the C-7 hydroxyl group of 10-O-acetyl-beta-rhodomycinone (16) and the C-10 hydroxyl group of the C-7,9-O-phenylboronate (14), respectively, in the presence of trimethylsilyl trifluoromethanesulfonate. Under the Königs-Knorr conditions, 16 was also glycosidated to provide a fluoro sugar analog (7).