Glucose dithioacetal, oxidation

Although periodates also oxidize polycyclic aromatic hydrocarbons, phenols, hydrazines, active methylene compounds and sulfides, chemoselectivity can usually be achieved and glycol cleavage oxidation takes precedence. For example, the diol moiety in the diethyl dithioacetal derivative of o-glucose can be selectively oxidized in good yield (equation 6). In contrast, LTA is less selective dum periodate and oxidizes a far greater variety of oiganic compounds. Consequently, in order to minimize undesired reactions, it is customary to add LTA slowly to avoid contact of die initially formed products widi an excess of the oxidant (equation 7). ... 

Hough, L, Taha, M I, The disulphones derived by oxidation of 2-amino-2-deoxy-D-glucose diethyl dithioacetal hydrochloride and its A-acetyl derivative with peroxypropionic acid, J. Chem. Soc., 3564-3572, 1957. 

MacDonald and H. O. L. Fischer372 oxidized D-glucose diethyl dithioacetal pentaacetate (24) and its D-manno isomer with mono-peroxyphthalic acid in ether, isolating not the epimeric disulfones but a common product, to which they assigned the structure 3,4,5,6-tetra- O - acetyl -1,2- dideoxy-1,1 -bis (ethylsulfonyl)-D-arabtno-hex-1-enitol (176). Ammonolysis of 176 and reacetylation afforded 177, which was also prepared by oxidation of 2-acetamido-3,4,5,6-tetra-0-acetyl-2-deoxy-D-glucose diethyl dithioacetal, whereas the action of hydrazine in methanol on 176 produced a retroaldol reaction (and saponification) affording D-arabinose (179, 40% yield) and bis(ethyl-sulfonyl)methane (178). The latter reaction accords with earlier ob-... 

Sulfones display strong absorption at 1355-1310cm" and 1160-1110cm" for S=0 stretching for example, the monosulfone obtained by oxidizing penta-0-acetyl-a/de/iydo-D-glucose dibenzyl dithioacetal has a band at 1305 cm" (Whiffen, 1957). 

A new, three-step synthesis of 1-deoxy-D-fructose (27% overall yield) is based on reductive desulphurization of 2-amino-2-deoxy-D-glucose diethyl dithioacetal to give 2-amino-l,2-dideoxy-D-glucitol, which was oxidatively deaminated using... 

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