Phosphorylation dihydrogen phosphate

A more complicated reaction sequence has been used by Ukita and Nagasawa (59) in their synthesis of 2-deoxy D-ribose 5-phosphate (2-deoxy D-erythro-pentose 5-(dihydrogen phosphate)), (29). They phosphorylated a mixture of the anomeric methyl deoxyribofuranosides (24)... 

Full details on the phosphorylation of water and alcohols by 4-nitrophenyl dihydrogen phosphate and the NfC H ) - and N(CH3) -salts of its mono- and dianion have been published 146>. Phosphoryl group transfer from the monoanion and dianion is thought to proceed via the monomeric POf ion. Addition of the sterically unhindered amine quinuclidine to an acetonitrile solution containing the phosphate monoanion and tert-butanol produces t-butyl phosphate at a faster rate than does the addition of the more hindered diisopropylethylamine. This nucleophilic catalysis of the phosphorylation reaction is also explained by the intermediacy of the POf ion. 

F. Trigalo, M. Level, and L. Szabo, Phosphorylated sugars. Part XVII. Synthesis of 3-deoxy-D-araWrco-[l-14C]heptulosonic acid 7-(dihydrogen phosphate), J. Chem. Soc., Perkin Trans. I, (1975) 600-602. 

Phosphorylation.1 Alkyl(phenyl) dihydrogen phosphates (3) are prepared conveniently in fair to good yield by the following sequence. The reaction of an alcohol (or phenol) with the reagent (1) in THF in the presence of pyridine at—20° and subsequent hydrolysis with water and a trace of pyridine at 15° yields the diester (2). The O-protective group in (2) is then eliminated by hydrolysis with pyridine—water at 80° to give (3). 

Trichloroethyl dihydrogen phosphate (2). This substance can be prepared as a crystalline solid (m.p. 120-121°) in good yield by the following procedure The alcohol and phosphoryl chloride are refluxed with a catalyst (AICI3, KCl, or pyridine) for 4 hr. (HCl is evolved). The resulting phosphoro-dichloridate (1) is then heated with a small excess of water for 1 hr. at 80°. 

Synonyms 3-[2-(dimethylajtmno)ethyI]-i/f-indol-4-ol dihydrogen phosphate ester O-phosphoryl-4-hydroxy-A JV-dimethyltryptamine Indocybin CY-39 Psilocybin 4-op-dmt... 

Steroids possessing one or two isolated or conjugated double bonds are converted into their dihydrogen phosphates when brought into contact with (l-phenyl-l,2-dibromoethyl)phosphonic acid in the presence of ethyldiisopropyl-amine. The reactions presumably involve monomeric metaphosphate ion as the effective phosphorylating agent. ... 

Fig. 11.1.9. Separation of a solution of adenosine and its phosphorylated derivatives. Chromatographic conditions column, Ultrasphere 5 /im ODS (250 x 4.6 mm) mobile phase, 0.05 M ammonium dihydrogen phosphate, pH 5.0 in methanol-water (10 90) flow rate, 1.9 ml/min detection, UV at 254 nm. Peaks 1, 5 -ATP and 5 -ADP 2, 5 -AMP 3, 2 -AMP 4, 2, 3 -cAMP 5, 3 -AMP 6, 3, 5 -cAMP 7, adenosine. Reproduced from Ramos and Schoffstall (1983), with permission.

Synonyms 3-[2-(Dimethylamino)ethylIindol-4-ol dihydrogen phosphate ester 0-phosphoryl-4-hydroxy-N,N-dimethyltryptamine indocybin Trade names ... 

A route to hept-2-ulosonic acid derivatives is available by way of the reaction of 2,3 4,5-di-0-isopropylidene-L-arabinose and 2,4 3,5-di-0-ethylidene-L-xylose with ethyl nitrosoacetate. ° Isomerization of the intermediate nitroso derivatives with alcoholic sodium nitrite yielded the corresponding oximes, which can be deoximated with lead tetra-acetate in acetic acid. 3-Deoxy-D-manno-oct-2-ulosonic acid 5-(dihydrogen phosphate) and its D-gluco analogue have been obtained by base-catalysed condensation of o-arabinose 2-phosphate (obtained by way of phosphorylation of benzyl 3,4-0-isopropylidene-P-D-arabinopyrano-side) with oxalacetic and separation of the isomers by ion-exchange chromato-graphy. ... 

Dimethylaminoethyl)-lH-indol-4-yl dihydrogen phosphate (jjsilocybin), the O-phosphoryl-4-hydroxy... 

In the quest for free metaphosphate, racemization has been observed for phosphoryl transfer from phenyl dihydrogen (R)-[ 0, " 0, 0]-phosphate to tert-butyl alcohol in MeCN. ... 

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