REACTIONS OF NITRO SUGARS .47. SYNTHETICALLY USEFUL TRANSFORMATIONS OF A BRANCHED-CHAIN, DEOXYNITRO-1-THIO-D-GLUCITOL, INCLUDING A NOVEL MODE OF 1-THIOGLYCOSIDE FORMATION

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. © 1990.