The key step of the synthesis involves the reaction of glycals [3,4,6-tri- O-acetyl- d-glucal ( 1), the new glycal derivative 4- O-acetyl-1,5-anhydro-2,6-dideoxy-3- C-methyl-3- O-methyl- l- ribo-hex-l-enitol ( 2), and 3-acetamido-4,6,-di- O-acetyl-1,5-anhydro-2,3-dideoxy- d- arabino-hex-l-enitol ( 3)] with 1.5 molar equivalents of several alcohols in the presence of N-bromosuccinimide in acetonitrile to give mainly the corresponding 2-bromo-2-deoxy-α-glycopyranosides ( 4-21). The glycopyranosides ( 4-8 and 16-21) from 1 and 3 have the α- d- manno configuration and those ( 10-15) from 2 have the α- l- altro configuration. The yields are high from 1, virtually quantitative from 2, and moderate from 3. Debromination of the 2-bromo-2-deoxy compounds with tributylstannane and a radical initiator gives the corresponding 2-deoxy-α-glycopyranosides ( 22-38) in quantitative yields. In particular, the branched-chain glycal 2 reacts with alcohols to give exclusively the corresponding α-glycopyranosides ( 27-32) of cladinose in strikingly high overall yields. The stereoselectivity and regiospecificity of the bromination reaction are described. 1,3-Dibromo-5,5-dimethylhydantoin and N-bromoacetamide are also found to be useful for the reaction.