Addition reactions to a 3,4-anhydroheptanose gave heptanoside analogues of carbohydrate derivatives in good to excellent stereochemical purity. Characterization of the products by (1)H and (13)C NMR, COSY, HSQC-DEPT, HMBC, 1D TOCSY, and NOE experiments were performed to obtain the stereochemistry of addition. The 3,4-anhydroheptanose used in this study is obtained from the ring-expansion of a cyclopropanated galactal and thus demonstrates the synthetic utility of heptanose synthesis via cyclopropanated carbohydrates.