SYNTHESIS OF 2 3-AMINO-2,3-DIDEOXYHEXURONIC ACID-DERIVATIVES

Methyl (methyl 3-acetamido-2,3-dideoxy-α-D-ribo-hexopyranosid)uronate was prepared from methyl 3-acetamido-4O-benzoyl-6-bromo-2,3,6-trideoxy-α-D-ribo-hexopyranoside (2) by a sequence or reactions involving photodecom̄position of the 6-azido-4-hydroxyl analog of 2, followed by successive mild hydrolysis of the intermediate imine 8 (to afford the aldehyde 11), oxidation, and esterification. In contrast, mild hydrolysis of the photoproduct (6) from the corresponding 6-azido-4-acetate proceeded with complete β-elimination to give, after oxidation and esterification, methyl (methyl 3-acetamido-2,3,4-trideoxy-α-D-glycero-hex-4 -enopyranosid)uronate. The intermediate imines (6 and 8) and corresponding aldehydes (9 and 11) were characterized as their crystalline 1,3-diphenylimidazolidine analogs, and aldehyde 9 further as the oxime. © 1979.