Glucopyranose phosphorylation

Deoxy-2-dimethoxyphosphoryl-D-glucopyranose (this usage of phosphoryl is given in [13], Section D, Rule 5.68, and [14], p. 65) or dimethyl 2-deoxy-D-glucopyranos-2-ylphosphonate... 

While this model explained the action of the brain enzyme on a number of hexose substrates and nonsubstrate inhibitory analogs, the mode had its weaknesses. It assumed that the other conformations of a hexose that are in equilibrium with the active conformer act as competitive inhibitors relative to this conformer. One cannot evaluate the effect of a competitive inhibitor which is present in a constant proportion relative to the active substrate by initial velocity measurements. Moreover, the use of apparent Michaelis constants may not provide accurate estimates of affinity, which is more directly related to a dissociation constant. The chief limitation of the model, however, is that an equally great number of experimental facts can be satisfactorily explained in terms of a simpler scheme involving the binding and phosphorylation of the Cl conformer. Furthermore, one can understand more directly how the enzyme can phosphorylate glucopyranose and fructofuranose equally well. 

It had been known from at least the time of Pasteur that the presence of sodium or potassium phosphate aided the progress of a yeast fermentation. Later intensive study showed that a complex group of enzymes (phosphatases and phosphorylases) was responsible for the phosphorylation, dephosphorylation and interconversion of D-glucose 6-phosphate, D-fructose 6-phosphate, D-fructose 1,6-diphosphate and similar substances in various types of cells and muscle tissue. Detailed reviews of the field are available. - A further advance was made in 1936, when Cori and Cori noted that in certain circumstances well-washed frog muscle immersed in a sodium phosphate buffer utilized the inorganic phosphate to produce a new hexose phosphate (the Cori ester). This compound was later shown to be a-D-glucopyranose-l-phosphate and yielded crystalline dipotassium and brucine salts. The Cori ester arose because... 

Phosphorylation of protected D-glucopyranose and D-galactopyranose with dioxaphosphorinane or 6-methyldioxaphosphorinane gave the corresponding glycosyl phosphorus derivatives (1). Similarly prepared were the phosphono-diamidite and benzyl phosphonoamidite derivatives (2) and (3). Treatment of... 

Phosphamides, A-Sulfates and Related Esters - 5- -,3-0-Cyclic phos-phamides have been prepared by reaction of 5-amino-5-deoxy-l,2-0-isopropyl-idene-a-D-xylofuranose with either phenylphosphonic dichloride or phosphoryl chloride, and their conformations determined. Chemo-selective -sulfation of 2-amino-2-deoxy-P-D-glucopyranose derivatives with a single free hydroxy-group was achieved with phenyl chlorosulfate followed by hydrolysis in aqueous NaHC03. ... 

Pused oxazollne derivatives (77) have been obtained in high yield upon attempted phosphorylation of 3, 6-trl-0-acetyl-2-acylamlno-2-deoxy-D-glucopyranoses with 2-chlorophenylphosphorodi-(1,2,4-trlazollde) in the presence of trlethylamine... 

I, 2-0-Isopropylidene-a-D-xylo- and -ribo-furanose each gave the two possible isomers of the corresponding cyclic 3,5-(phenyl phosphate) when treated with phenyl phosphorodichloridate, but only one isomer was formed on phosphorylation of the former compound with bis-(2,2,2-trichloroethyl) phosphorochlori-date. The synthesis of a new type of branched-chain sugar phosphate, trans-3-C-cyanomethylene-3-deoxy-l,2-0-isopropylidene-a-D-erythro-pentofuranose 5-[bis-(2,2,2-trichloroethyl) phosphate], was also reported. 2,3,4,6-Tetra-0-acetyl(or benzoyl)-P-D-glucopyranose reacted with tris(dimethylamino)phosphine and carbon tetrachloride to give both anomeric oxyphosphonium chlorides (see Vol. 9, p. 48), which afforded 1,2-orthoesters with alcohols or a mixture of phenyl 1-thio-D-glucopyranosides with thiophenol. Similar treatment of 2,3,4,6-tetra-... 

Syntheses of the 4-phosphates of D-glycero-D-gulo-heptose (Scheme 32) and D-glycero-L-manno-heptose have been reported by similar routes. Phosphorylation of W2Hco-inositol with polyphosphoric acid gave the hexakisphosphate, whereas epMnositol afforded a tetrakisphosphate only. The contents of inositol cyclic 1,2-phosphate and p-glucopyranose 1- and 6-phosphates in extracts from brain tissues have been determined by g.l.c. of the trimethylsilylated... 

The product of phosphorylation of 5,6-protected ascorbic acid has been shown to be the 2- -phosphate by X ray analysis of its dipiperazinium salt dihydrate.Four 2-acylamino-2-deoxy-1,3 4 tri- -dodecanoyl- -D-glucopyranose 6-phosphate analogues (25) of the repeating unit of the glycophospholipid "Lipid A" have been synthesized. An alternative route has been described for the... 

The species Arenibacter certesii has a LOS that contains several phosphorylated sugars and rhamnose, and Lipid A is formed starting from the P-4-/3-D-DAG-(l-6)-a-D-GlcN-l-a-P disaccharide in which DAG is 2,3-diamino-2,3-dideoxy-/3-D-glucopyranose (Silipo et al, 2005c). 

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