Chemical syntheses of six α-linked disaccharides are described, namely, 6-O-(α-D-glucopyranosyl)-D-galactose (1), 6-O-(α-D-galactopyranosyl)-D-galactose (2), 6-O-(α-D-talopyranosyl)-D-galactose (3), 3-O-(α-D-glucopyranosyl)-D-glucose (nigerose) (4), 3-O-(α-D-galactopyranosyl)-D-glucose (5), and 3-O-(α-D-talopyranosyl)-D-glucose (6).