Phosphates and Related Esters

A review of phosphates and phosphonates of biochemical interest includes some carbohydrate examples. A theoretical study has been carried out to determine the anomeric effect of phosphate groups (see also Chapter 21). Enzymic syntheses of sugar phosj hates are included in a review of enzymes in organic chemistry. 

Treatment of potato peels with phosphorylase gave D-glucose which was phosphorylated to yield D-glucose 1-phosphate of commercial grade. A preparative enzymic synthesis of D-threo-2-pentulose 

The glucose phosphate derivatives (24.) have been synthesized 

Dimethylphosphates (25) - (27) of deoxy sugars have been prepared by 

Relatively fast phosphate migration has been observed in ribo- 

Methods for the synthesis of phosphate monoesters and phosphoramidates of carbohydrates and nucleic acids have been reviewed.  

Reagents i, HBr-HOAc ii, EtOH-jy/w-collidine iii, HjPO, iv, NaOMe-MeOH 

Reagents i, DMSO-DCC-PyHCl ii, PhjP=CHPO(OPh)j iii, Hj-PtOj iv, H,0+ 

6- 0-isopropylidene-L-ascorbate. The product at pH 12—13 in high concentration of pyridine was quantitatively the 2-phosphate. Hydrolysis of the acetal gave a 70% yield of L-ascorbate 2-phosphate. In the absence of pyridine the products were the 2-phosphate and the diphosphate (24).  

6- Dideoxy-6-phosphono-D-ara6/ o-hexose (25), an isosteric analogue of D-arabinose 5-phosphate, has been synthesized. l,2-0-Isopropylidene-6-thio-a-D-glucofuranose reacted with phosphorus trichloride-triethylamine in absolute ether to give the 3,5,6-bicyclothiophosphite (26).  

Considerable attention is given to phosphate ester and related chemistry in Chapter 20. The aldolase-catalysed synthesis of monosaccharides by way of phosphate intermediates is covered in Chapter 2. 

A procedure for the preparation of a-D-glucose 1-phosphate by a-glucanphos-phorylase-catalysed degradation of starch has been developed. Tri-O-acetyl-a-L-rhanmopyranosyl dialkylphosphates 26 and similar, O- nzyl protected deri- 

Phosphoramidon (33), an inhibitor of the endothelin-converting enzyme, and the glycosylated phosphatidylcholines 34, which are closely related to a newly dicovered, natural fungicide, have been synthesized by use of the phosphorodi-chloridate method. 

A convenient synthesis of glucose 1,6-bisphosphates with H-, C-, P-or P-labels is based on the hexokinase-catalysed formation of glucose 1 phosphate from appropriately labelled D-glucose and ATP, followed by phospho-glucomutase-mediated equilibration to the bisphosphate and D-glucose.  

2-0-Phosphorylated furanose derivatives, such as compounds 36, were obtained in hi yields by exposure of alcohol 35 to dialkyl phosphorochloridates in the presence of 1-methylimidazole. Triphosgene-mediated coupling of phos-phonic acid with suitably protected nucleosides produced nucleoside-3 -H-phos-phonate monoesters, e.g. compound 37, in good to excellent yields. 6-Chloro-6-deoxy-l,2-0-isopropylidene-a-D-glucofuranose 3,5-cyclophosphorochloridate (38) has been converted to the novel cyclophosphates 39.  

Xylitol 1-0-(dichlorophosphite)-2,3 4i5-bis-O-(chlorophosphite), L-arabinitol 1-0-(dichlorophosphite)-2,3s4i5-bis-O-(chlorophosphite), and ribitol 3-0-(dichlorophosphite)-1,2 4 5-bis-0-(chlorophosphite) have been prepared by reaction of pentitols with phosphorus trichloride.  

0 isotope effect on hydrolysis of D-glucose 6-phosphate labelled with 0 in the non-linking phosphate positions has been determined. Using glucose and [1- Cjglucose esters, the hydrolysis was stopped at half reaction and the unreacted ester was enzymically converted to ribulose 5-phosphate and carbon 

D-Glucosyl dibenzylphosphates, (29) - (31) have been prepared by reaction of the corresponding (-glycosyl bromide with silver di-benzylphosphate and their reactions towards sodium azide investigated. Monodebenzylation occurred in each case and sulphonates at C-6 were displaced but 4-0-sulphonates were unreactive. Thus the 6-tosylate (29) gave the azide (32), the 4,6-dimesylate (30) gave the 6-azido-4-O-mesyl product (33), whereas the 4-0-mesylate (31) did not 

All four monodeoxyfluoro- C-D-glucopyranosyl phosphates have been prepared using the DAST procedure and their acid-catalyzed hydrolysis 

Total synthesis of optically active myo-inositol 1,4,5-triphosphate is described in Chapter 18. 

Cold plasma reaction (see also Chapter 2, ref. 13) of methane-water mixtures in the presence of apatite yielded some glucose 6-phosphate and ribose 

Triose, tetrose, and pentose phosphates enriched with C have been prepared by the Kiliani-Fischer reaction on the terminal phosphates of the next lower aldose. The mixed nitriles were separated on Dowex 1-X8 resin and reduced with hydrogen over Pd-BaS04. The synthesis of D-glucose 2-phosphate by phosphorylation of l,3,4,6-tetra-0-acetyl-j3-D-glucopyranosyl chloride, itself prepared by 2 1 acetyl migration, has been reported. Rates of phosphate hydrolysis in 0.25 M sulphuric acid and in 0.25 M sodium hydroxide were measured for D-glucose monophosphates in the former the order was 1-phosphate 2-phosphate 3-phosphate 6-phosphate while in the latter it was 3-phosphate 6-phosphate 2-phosphate 1-phosphate.  

Opening of orthoesters with phosphoric acid and its derivatives has been used to prepare glycosyl phosphates.Thus 3,4,6-tri-O-acetyl-a-D-gluco-pyranose 1,2-orthoacetate reacted with decyl, tridecyl, pentadecyl, and hexa-decyl monobenzyl phosphates to give the ]8-l-phosphate derivatives (11). 

Suzuki, K. Tokutome, and N. Taguchi, Waseda Daigaku Rikogaku Kenkyusho Hokoku, 1977, 79, 50 (Chem. Abs., 1979, 90, 23 426r). 

6-Phosphatidyl-D-glucose (13) and its thiophosphate analogue have been prepared by reaction of the amidite (14) with 1,2,3,4-tetra-O-acetyl-D-gluco-pyranose followed by oxidation of P to P by nitric oxide (or sulphur), deprotection of the glyceryl and phosphate groups, acylation with stearoyl 

A review of the methods for preparing isotopically enriched glycosyl phosphates and nucleoside diphosphates also covers enzymic preparations and solution conformations. A method for synthesizing aldosyl phosphates involving oxidation of the 

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 methyl 4-0-phosphono (28) and 4--0-(/3-D-glucopyranosyl), (29), derivatives of 3-deoxy-/3-D-erythro-2-hexulopyranosidonic acid, and the 3-0-phosphono, and 3- -(/ D-glucopyranosyl) derivatives of 2-deoxy-K-D-arabino-hexopyranose have been synthesized and their behaviour in acidic media examined. 

Glycoamidophosphites in the pentose series based on methyl 2,3-0-i s opr opylidene-/d-D-ribofurano side, 1, 2-0-isopropylidene-i -D-xylofuranose, xylitan, and 3,5- -isopropylidene-xylitan were synthesized, and some were used as ligands for palladium complexes. The 

Several phosphorylations of nucleosides are referred to in Chapter 20, and the use of protected 1-dibenzylphosphates as glycosyl donors under neutral conditions is covered in Chapter 3. 

6-Tetra-O-acetyl-P-D-gluco- and -galactopyranosyl H-phosphonates were converted into citronellyl and dolichyl glycosyl phosphates by reaction with the respective alcohols, followed by oxidation and deacetylation,and dolichyl p-D-mannopyranosyl phosphate was prepared by reaction of a protected a-D-manno-pyranosyl bromide with dolichyl phosphate. Ceramide-1-phosphate sugars, e.g., P-D-Glc/ -0P03-Cer, a new type of glycophospholipid, have been obtained 

Experiments with an 0-labelled sugar indicated that the UDP-JV-acetylgluco-samine 2-epimerase-catalysed equilibration of UDP-GlcNAc with UDP-ManNAc proceeds via 2- acetamido-D-glucal.  

X-Ray irradiation of polycrystalline sodium and barium salts of D-glucose 1-and 6-phosphate and of D-ribose 5-phosphate produced P03 radicals, as evidenced by ESR spectroscopic studies no precursor phosphoranyl radicals were detected.  

Phosphorylated lipophilic derivatives of ara C as potential pro-drugs, spin-labelled ATP derivatives and phosphorylation products of 5 -AMP are referred to in Chapter 20, inositol phosphate derivatives in Chapter 18, and H-labelled Lipid A analogues in Chapter 3. Analogues of 2-deoxy-D-ribose with phosphorous in the ring are covered in Chapter 17. 

Reagents i, ROH, PivCI, Py, THF ii, A/,Obis(tms)-trifluoroacetamide iii, BHa-amine complex 

The tritiated benzophenone-containing derivative of glucose 6-phosphate 23 was made as a photoactivatible affinity label for proteins. Phosphonate 24 was prepared to act as a hapten to elicit monoclonal antibodies for transesterification reactions between 25 (R = H) and 26 however, the antibodies failed to catalyse the reaction. D-Galactose 6-0-phosphate and 0-thionophosphate monoesters 27 have been prepared and then deacetalated by heating in water without added acid.  

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Carboxylic Esters Sulphonate Esters Phosphate and Related Esters Other Esters... 

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