Nucleoside Phosphates and Phosphonates

As usual, standard syntheses of nucleotides are not included here. 

A review on the synthesis of phosphodiesters by the cyclic enediol phosphate method includes syntheses of phosphatidyl sugars and nucleosides. In reports of plenary lectures, Reese has discussed 

Bis-3 - 5 -cyclic dinucleotides of type (48) havebeen synthesized they are competitive inhibitors of DNA-dependent RNA polymerase of E. coli.  

Analogues of cyclic AMP derived from the carbocyclic nucleosides aristeromycin and neplanocin have been prepared by intramolecular phosphodiester bond formation catalysed by divalent lead ions, and studies have been reported on the synthesis and biological activity of nucleoside 3, 5 -cyclic phosphotriesters and phosphoramidates.  

Enzymic phosphorylation has been used to prepare 5 -phosphates 

Triethylammonium salts of aryl H-phosphonates have been coupled to the 3 -OH of deoxynucleosides using pivaloyl chloride as condensing agent subsequent hydrolysis by aqueous pyridine gives nucleoside H-phosphonate building blocks 

As regards modified intemucleotidic links, bis(deoxynucleosidyl)-long-chain alkyl triphosphates have been reported, along with thymidine linked via either 0-3 or 0-5 to 0-6 of methyl a-D-glucopyranoside through a hydrophobic phosphotriester. A known derivative of 3 -deoxy-3 -C-formylthymidine (Vol. 28, p. 277-8) has been converted into a phosphoramidite which was used to make oligomers with a five-atom phosphate link, as in 178.  

Triesters 183 (R=Me, Bu Ph) have been prepared by S-alkylation of the bis(thymidylyl) phosphorodithioate. The species 183, particularly with R=Me, were rapidly converted back to the phosphorodithioate using various cell extracts, raising the possibility of using the 5-acylthioethyl (SATE) blocking group in delivery of antisense oligonucleotides containing phosphorodithioate units.  

There has been interest in methylphosphonate analogues of intemucleotidic linkages. Work in this area in Stawinski s laboratory has been reviewed, together 

Reagents i, 3 -0-Tbdms-thymidine ii, 5 -0-Tbdms-thymidine, 2-bromo-4,5-dicyanoimidazole iii, 3-H-1,2-benzodithiol-3-one 1,1 -dioxide 109 iv. TFA 

As in previous volumes, standard syntheses of oligonucleotides are not discussed. A review has appeared (in Czech) on chemical and enzymic synthesis of P-labelled nucleoside mono-, di- and triphosphates and 2 -deoxynucleoside phosphates. 

The spin-labelled 2 -deoxyadenosine derivative (68) has been prepared. 

A series of 3 -phosphoreonidite derivatives of 2 -deoxyribo-nucleosides protected at 0-5 have been synthesized in connection with oligonucleotide synthesis,and the non-aqueous oxidation of nucleoside phosphites to phosphates has been studied, with bis- 

Treatment of cyclic AMP tributylammonium salt with alkyl 

Two good methods have been developed for the synthesis of 2 - 

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Carbocyclic Nucleoside Analogues Nucleoside Phosphates and Phosphonates Ether, Acetal, and Ester Derivatives Miscellaneous Nucleoside Analogues Reactions... 

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