2-Cyanoethyl phosphate phosphorylation with

Attempts to perform the phosphorylation step with either pyrophosphoryl chloride or 2-cyanoethyl phosphate failed. ... 

Deoxycytidine was fully acylated with anisoyl chloride in pyridine to (117), and this was converted into A -anisoyl-2 -deoxycytidine (118). The mono-O-acyl derivative was treated with chloro-bis(p-methoxyphenyl)-phenylmethane (119) in pyridine, to yield 120, which was phosphorylated with 2-cyanoethyl phosphate and (65) in pyridine to the phospho-diester (121) in high yield. Removal of the protecting groups was achieved in two ways. One method involved the treatment of (121) with aqueous ammonia to give (122) which, on treatment with 80% acetic acid at room temperature for twenty minutes, afforded 2 -deoxycytidine 3 -phosphate... 

Uridine 3 -phosphate (147) was prepared by Hall and Thedford by the phosphorylation of 2, 5 -di-0-trityluridine with 2-cyanoethyl phosphate and iVjiV -dicyclohexylcarbodiiinide to give the diester (146). This diester was de-esterified with alkali, and then hydrolyzed with 80% acetic acid at 100° for 90 minutes, to give (147). The structure of (14S) had been rigorously established by Yung and Fox, who methanesulfonated (145) to obtain (148). Treatment of (148) with sodium benzoate in N,N-di-methylformamide gave the 2,3 -anhydronucleoside (149). The anhydro... 

D-lyxofuranosyl)uracil (185) with 2-cyanoethyl phosphate and N,N -dicyclohexylcarbodiimide to give the 2 (3 )-phosphates (186), which were converted into l-/S-D-lyxofuranosyluracil 2 3 -cyclic phosphate (187). Conversion of (185) into (188) was accomplished by a five-step process (acetonation, debenzoylation, phosphorylation, deacetonation, and de-cyanoethylation). Treatment of (188) with J r,i T -dicyclohexylcarbodi-imide in pyridine gave a mixture of the 3 5 - and 2 5 -cycIic phosphates (189) and (190) of l-j3-D-lyxosyluracil, which differed in properties from the 2 3 -cyclic phosphate derivative (187) and did not consume metaperiodate. These cyclic phosphates (189) and (190) were separated. Only one of them was converted into the other by mild treatment with acid... 

Chemical Synthesis.—Purine nucleoside 5 -monophosphates enriched with or 0 on the phosphate group are conveniently prepared by treating phosphorus pentachloride in dry triethyl phosphate with one equivalent of the appropriately labelled water to give PO]- or P 0]P0Cl3, which is not isolated but mixed with adenosine or guanosine in the same solvent. Work-up of the resulting 5 -phos-phorodichloridate in similarly labelled water permits the formation of pO]-or P 0]AMP (or GMP) in fair yield with good enrichment. The 5 -monophos-phates of the 5 -C-methyl uridines derived from 6-deoxy-D-allose and 6-deoxy-L-talose have been prepared via phosphorylation of the 2, 3 -0,0-ethoxymethyl-idene derivative of the nucleosides (1) with -cyanoethyl phosphate and DCC or TPS-Cl. The same method has been used to phosphorylate iV -benzoylated 2, 3 -0,C -isopropylidene derivatives of various 5 -C-alkyladenosine species (2) and also 4 -allyladenosine (3) as part of a study in which derivatives of AMP... 

Blocked pyridine nucleosides have been phosphorylated with (3-cyanoethyl phosphate anddicyclohexylcarbodiimide, diphenyl phosphorochlori-date, and with triethyl phosphate followed by oxidation. ... 

Dicyclohexylcarbodiimide Phosphorylation with 2-cyanoethyl phosphate OH OPOgHg... 

The reaction of phosphine with aliphatic aldehydes is a useful method of C-P bond formation Dialkyl phosphites are smoothly converted to pyrophosphates with nitrosyl chloride . 2-Cyanoethyl phosphate has been introduced as a phosphorylating agent in the nucleotide field. The cyanoethyl group can be removed under mild alkaline conditions, which do not affect the essential part of the nucleotide . 

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