Synthetically useful transformations of a branched-chain, deoxynitro-1-thio-D-glucitol, including a novel mode of 1-thioglycoside formation

Article abstract of DOI:10.1016/0008-6215(90)80144-R

2-Deoxy-3,4;5,6-di-O-isopropylidene-2-C-(nitromethyl)-1-S-phenyl-1-thio-D-glucitol (2), obtainable from D-mannose in several steps with good overall yield, was converted into the corresponding sulfoxide, α-chlorosulfide, α-acetoxysulfide, and analogous 2-C-(acetamido)methyl derivatives.Mild hydrolysis of the 1-chloro derivative of 2 gave a 2-deoxy-2-C-methylene-aldehydo sugar 3,4;5,6-diacetal by concomitant elimination of nitrous acid, whereas a 2-deoxy-2-C-(nitromethyl)-D-glucitol 3,4;5,6-diacetal was obtained under reducing conditions.Pummerer rearrangement of the sulfoxide derived from 2 gave, depending on the reaction conditions, the corresponding α-acetoxysulfide or phenyl 2-deoxy-2-C-(nitromethyl)-1-thio-β-D-glucopyranoside 3,4,6-triacetate.