Branched-chain aminodeoxy sugars. Methyl 3-<i>C</i>-aminomethyl-2-deoxy-α-<scp>D</scp>-<i>ribo</i>-hexopyranoside and methyl 3-<i>C</i>-aminomethyl-2-deoxy-α-<scp>D</scp>-<i>arabino</i> hexopyranoside

Abstract

Addition of methyl 4,6-O-benzylidene-2-deoxy-α-D-erythro-hexopyranosid-3-ulose (1) to excess nitromethane and 1 molar equivalent of sodium methoxide in methanol gave methyl 4,6-O-benzylidene-2-deoxy-3-C-nitromethyl-α-D-ribo-hexopyranoside (2) and the arabino stereoisomer 3 in 63 and 22% yields, respectively. The proof of structure of the branched-chain deoxy nitro sugars is described. Debenzylidenation of the nitro sugars afforded the partially blocked nitro sugars 4 and 5. Catalytic hydrogenation of the latter or of 2 and 3 yielded the branched-chain aminodeoxy sugars 7 and 9 (7 characterized as its N-acetyl derivative and 9 as its N-2,4-dinitrophenyl derivative).