title: On Moffatt dehydration of glucose-derived nitro alcohols.
abstract: Moffatt dehydration of 1,2:5,6-di-O-isopropylidene-α-d-glucofuranose derived nitro alcohols with a mixture of Ac(2)O and DMSO was reinvestigated. It was discovered that, regardless of the absolute configuration at C(3) of the sugar moiety, the dehydration provided exclusively the (3Z)-nitromethylene derivative. Slight modification of the workup conditions (pH⩾8, temperature: 25-30°C) gave exclusively a novel product, (3S)-3-deoxy-3-methylthio-3-C-nitromethyl-1,2:5,6-di-O-isopropylidene-α-d-glucofuranose. The latter was obtained by a Michael addition of thiomethylate anion to the previously reported nitromethylene derivative during the aqueous basic workup at ambient or slightly elevated temperature. The putative mechanism leading to the thiomethylate anion includes Pummerer rearrangement of DMSO and basic hydrolysis of thus formed methylsulfanylmethyl acetate.
authors.affiliation: Faculty of Material Science and Applied Chemistry, Riga Technical University, 14/24 Azenes Str., Riga, Latvia.
authors.forename: Jevgeņija
authors.initials: J
authors.lastname: Lugiņina
authors.forename: Vitālijs
authors.initials: V
authors.lastname: Rjabovs
authors.forename: Sergey
authors.initials: S
authors.lastname: Belyakov
authors.forename: Māris
authors.initials: M
authors.lastname: Turks
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D005947:Glucose / Q000737:chemistry*; D009574:Nitro Compounds / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000438:Alcohols; D009574:Nitro Compounds; D005947:Glucose