Phosphorylation of D-glucose derivatives with inorganic cyclo-triphosphate: substituent effect at the 5-CH2OH or 2-OH group

The phosphorylation of several D-glucose derivatives has been achieved using inorganic sodium cyclo-triphosphate hexahydrate (P3m), Na3P3O9 x 6H2O, in aqueous solution. In the phosphorylation of D-glucuronic acid, 6-phosphoryl-D-glucose and D-xylose, beta-D-glucuronic acid 1-triphosphate, 6-phosphoryl-beta-D-glucose 1-triphosphate and beta-D-xylose 1-triphosphate were synthesized stereoselectively with maximum yields of 43.5, 32.8 and 41.9%, respectively. In the case of D-glucosamine and 2-deoxy-D-glucose, the main phosphorylated products were assigned to beta-D-glucosamine 1-triphosphate and 2-deoxy-beta-D-glucose 1-triphosphate by 1H-, 13C- and 31P-NMR, and the yields were 13.9 and 13.4%, respectively.     

Phosphorylation of disaccharides with inorganic cyclo-triphosphate in aqueous solution

The phosphorylation of disaccharides by inorganic cyclo-triphosphate (P(3m)) with a six-membered ring was examined in aqueous solution. In the phosphorylation of cellobiose, lactose, and alpha,alpha-trehalose with P(3m), beta-D-glucopyranosyl-(1-->4)-beta-D-glucopyranosyl 1-triphosphate, beta-D-galactopyranosyl-(1-->4)-beta-D-glucopyranosyl 1-triphosphate, and 3-O-triphospho-alpha-D-glucopyranosyl-(1-->1)-alpha-D-glucopyranoside were synthesized with maximum yields of 28%, 35%, and 20%, respectively. In the reactions of maltose and sucrose with P(3m), two phosphorylated products were obtained in yields of 42% and 58%, respectively. The main phosphorylated products were assigned to alpha-D-glucopyranosyl-(1-->4)-beta-D-glucopyranosyl 1-triphosphate and beta-D-fructofuranosyl-(2-->1)-2-O-triphospho-alpha-D-glucopyranoside by heteronuclear multiple bond correlation (HMBC) NMR. The phosphorylation mechanism of disaccharides with P(3m) is discussed.     

Phosphorylation of nucleoside derivatives with aryl phosphoramidochloridates

The preparation of three aryl phosphorocyclohexylamidochloridates (7a, 7b and 7c) and an aryl phosphoromorpholidochloridate (8) is described. These aryl phosphoramidochloridates react with 2′,3′-O-methoxymethylene-uridine, -4-N-anisoylcytidine and -6-N-anisoyladenosine (9a, 9b and 9c, respectively), in the presence of the 1-ethylimidazole derivative (11a) to give high yields of the corresponding fully-protected 5′-phosphoramidates (10). Treatment of the latter compounds with aqueous alkali gives the nucleoside 5′-phosphoramidate derivatives (14) which, on mild acidic hydrolysis, give the corresponding unprotected 5′-nucleotides (15) in virtually quantitative yields. Phosphorylation of 2′-O-methoxytetrahydropyranyluridine (12) with 7a and 8, under the same conditions, occurs regiospecifically to give the corresponding 5′-phosphoramidate derivatives (13). The partially-protected dinucleoside phosphate (16b) has been prepared and phosphorylated with 7a to give, after removal of the protecting groups, the dinucleotide (18, pUpU) in high yield.     

Phosphorylation of 5'-deoxy-5-fluorouridine with inorganic phosphorylating agents

The phosphorylation of 5'-deoxy-5-fluorouridine (doxifluridine, 5'-DFUR) has been achieved using inorganic cyclo-triphosphate (P(3m), Na(3)P(3)O(9)) and monoimido-cyclo-triphosphate (MCTP, Na(3)P(3)O(8)NH) in aqueous solution. In the reaction of 5'-DFUR with P(3m), 2'-monophospho-5'-DFUR and 3'-monophospho-5'-DFUR were synthesized with a total yield of more than 95%. In the reaction of 5'-DFUR with MCTP, 2'-diphosphoramidophosphono-5'-DFUR and 3'-diphosphoramidophosphono-5'-DFUR were synthesized with a total yield of more than 40%. The phosphorylated products with P(3m) and MCTP were stable in neutral and alkaline solutions.     

Phosphorylation of trihydroxybenzenes with the trivalent phosphorus derivatives

Phosphorylation of the simplest trihydroxybenzenes and their acylated derivatives with the trivalent phosphorus reagents of cyclic and acyclic structure was discussed. A possibility of the selective phosphorylation of acylated trihydroxybenzene derivatives was demonstrated. A dismutation was detected, leading to dimers of the linear structure containing a variety of phosphorus-containing fragments of different nature.     

Phosphorylation of aminomethylated derivatives of 2,7-dihydroxynaphthalenes

Phosphorylation of 2,7-dihydroxynaphthalene derivatives, containing different amine components was performed by full amides of phosphorous acid. A substantial effect of the intramolecular hydrogen bond on the process of phosphorylation was shown. Cyclophosphorylation was performed and principal possibility of the synthesis of naphthophosphacrownaphanes having aminomethyl linkers was shown. Mannich aminomethylation of naphthophosphacyclophanes was found to be impossible.     

Phosphorylation of 1,4-bis(hydroxymethyl)benzene with trivalent phosphorus derivatives

Phosphorylation of 1,4-bis(hydroxymethyl)benzene with complete phosphorous acid amides and phenyl phosphorodichloridite is studied. Some phosphorus-containing linear systems, the phosphamacrocycle precursors, are synthesized. The possibility of synthesis of phosphamacrocyclic systems based on 1,4-bis(hydroxymethyl)benzene is considered; it was shown that this compound does not tend to form macrocycles.     

Diastereoselective synthesis of D- and L-myo-inositol 3,4,5,6-tetrakisphosphates from D-glucose via dihydroxylation of (+)-conduritol B derivatives

Syntheses of D- and L-myo-inositol 3,4,5,6-tetrakisphosphates were achieved via diastereoselective 1,2-addition of vinylcopper reagent with the chiral aldehyde prepared from 1,2,5,6-diisopropylidene-D-glucose, ring-closing metathesis of 1,7-diene with Grubbs catalyst followed by catalytic OsO(4) dihydroxylation of (+)-conduritol B derivatives.     

Carbohydrate Phosphorylation with Diphenylphosphorochloridate

In connection with the synthesis directed toward 25-hydroxycholesterol,^1/ and other cholestane derivatives hydroxylated in the side chain, the research was undertaken in order to find the most effective method for the preparation of pregn-17/20/-en-21-oic acid derivatives.^2/ In the present communication we would like to report the observation that contrary to the literature data, such pregnenoic acid derivatives can be conveniently obtained in very good yields by the Wittig-Horner reaction of 17-ketoandrostane derivatives and estrone with trialkyl phosphonoacetates when alcohols or DME are used as the reaction medium. In the previous reports the following statements have been made: 1/ the Wittig-Horner reaction of steroidal 17-ketones with trialkyl phosphonoacetates is compleetely inhibited as a result of the steric shielding of the carbonyl group^3a, 2/ this reaction gives very low yields^3b/, 3/ in the case of 17-ketoanderostane derivatives this reaction requires drastic conditions and is completely inhibited in the case of estrone/irrespective of conditions/^3c/.     

Phosphorylation of derivatives of β‐dialkyaminocrotonitriles with phosphorus(III) halides

The reaction of β‐dialkylaminocrotontriles with phosphorus(III) halides has been investigated. The basicity of the dialkylamino group influences the phosphorylation markedly, with pyrrolidine being the amine of choice. It was found that a solvent and the ratio of triethylamine play a significant role in phosphorylation. Although chloro‐ and dichlorophosphine derivatives proved impossible to separate as individual compounds; their solutions can be successfully used for further transformations. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:194–201, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20532     

Regioselective phthalation and succinylation of D-glucose and D-galactose using protecting groups: Conversion of the products to organotin derivatives

1,2: 5,6-Di-O-isopropylidene-α-D -glucofuranose was acylated at the free 0-3 position with phthalic and succinic anhydrides. Removal of the protecting groups gave the 3-O-acylglucopyranose compounds which were converted to their acetyl and organostannyl derivatives. A similar sequence of reactions was carried out with 1,2:3,4-di-O-isopropylidene-α-D -galactopyranose.     

Reaction of yeast inorganic pyrophosphatase with inorganic phosphate labeled with radioactive phosphorus

Conclusions The reaction of yeast inorganic pyrophosphatase with inorganic [p³²]phosphate forms a phosphorylated enzyme.     

Phosphorylation of chitosan with hexamethylphosphorous triamide

Russian Journal of General Chemistry -     

Phosphorylation of β-Cyclodextrin with Diphenylchlorophosphine

Russian Journal of General Chemistry -