The methyl β-glycoside of the title sugar, obtained from 2-deoxy-2-fluoro-β-d-glucopyranose tetraacetate by a sequence with detailed characterization of all intermediates, was converted by acetolysis–bromination into 3,4-di-O-acetyl-2,6-dideoxy-2-fluoro-α-l-talopyranosyl bromide, coupling of which with (7S,9S)-4-demethoxydaunomycinone afforded the 3,4-diacetate of 4-demethoxy-9-O-(2,6-dideoxy-2-fluoro-α-l-talopyranosyl)daunomycinone (19). The antitumor-active 19 was converted by way of its 14-bromo derivative into the 14-hydroxy analogue, the antitumor-active 4-demethoxyadriamycinone glycoside 21.