Synthesis of Cytidine 5'-Diphosphate and Guanosine 5'-Diphosphate¹

Advances in the Chemistry of Carbodiimides

“…In 1953, Khorana and Todd (333,341) demonstrated the power of carbodiimides to condense mono-and diesters of phosphoric acid to the corresponding diand tetraesters of pyrophosphoric acid. phosphates (44, 150, 200, 340, 530, 711, (113,116,474,475,589,776), and mixed anhydrides (45,46,386,428,450,575,582,757,871). This technique has contributed greatly to progress in the nucleotide field in recent years.…”

Chemistry of the Nucleotides

“…Further reaction of adenosine-S'-pyrophosphate with benzyl hydrogen N-cyc1ohexyl phosphoramidate gave the monobenzyl ester of adenosine-5' triphosphate (156), In an alternate approach, Chambers & Moffatt (158) developed syntheses of nuc1eoside-5'-phosphoramidates by the action of dicyc1ohexy1carbodiimide on a mixture of the nucleotide and primary or secondary base. In addition to the synthesis of nucleoside-S'-pyrophosphates (159,160) and -triphosphates (161), these intermediates proved useful for the synthesis of diesterified pyrophosphates, such as uridine diphosphate glucose (155), uridine diphosphate-glucuronic acid, and guanosine diphos phate-mannose (162), from the appropriate nucleoside phosphoramidate and sugar phosphate. In the same way, reaction of dicyclohexylguanidinium adenosine-5'-phosphoramidate with riboflavin-5'-phosphate gave flavin adenine dinucleotide (155).…”

Templated polymerizations on solid supports mediated by complementary nucleoside interactions

“…Polymerizations of the four different monomers (1-4) with the Wang resin solid support initiator 11 were carried out using copper(I) bromide as a catalyst and N-(n-propyl)-2-pyridylmethanimine as ligand in toluene in which the Wang resin has good swelling properties (Scheme 3). 41 In all cases, a mass increase after polymerization was observed, 180, 220, 240 and 120% for the polymerization of 1, 2, 3 and 4, respectively. The polymerizations were followed by IR spectroscopy ( Fig.…”

“…Cytidine was reacted with methacryloylacetone oxime in the presence of C. antarctica lipase 40 (Novozyme 435®) in dioxane and the product 5 was then protected as the 2′,3′-acetonide 41 3 in reasonable yield (ESI †). Unlike Moris and Gotor's original report 40 we found this enzyme-promoted reaction 42 to allow direct 5′-O-acylation of cytidine.…”