Cytidine 2 ,5-anhydro

Acid hydrolysis of cytidine ribitol pyrophosphate led to a series of products, depending on the conditions of hydrolysis. L-Ribitol 1-phosphate (n-ribitol 5-phosphate), isomeric ribitol phosphates formed by acid-catalyzed migration of the phosphate group from the terminal position, and 1,4-anhydro-DL-ribitol were isolated. 

However, synthesis of 2, 3 -anhydro-cytidine 70 could not be realized in this way, since treatment of the corresponding cyclic sulfite 69 with bicarbonate afforded the D-n fco-derivative 72. The initially formed epoxide 70 was opened with the oxygen atom from the heterocyclic moiety and this anhydro derivative 71 upon another ring-opening process with a bicarbonate anion provided 72 (O Scheme 21) [51]. 

Anhydro-2, 3 -O-isopropylideneadenosine iodide Adenosine 3, 5 -phosphate, P,0-ethyl ester, monohydrate N -[(Carboxymethyl)aminocarbonyl]adenosine (Glycylglycinato)copper(II)cytidine, dihydrate... 

Methylcytidine (correction to previous paper), platinum complex of cytidine 3 -phosphate, l- 3-D-arabinofuranosylcytosine 5 -phosphate (2 independent analyses), 2,2 -anhydro-l-/3-D-arabinofuranosyl-5-dimethylsulphonio-6-oxocytosine chloride, 2,2 -anhydro-l-(3, 5 -di-0-acetyl-j3-D-arabinofuranosyl)-5-chloro - 6 - oxocy tosine, 2,l -anhy dro -1 - - D -arabinofuranosylcy tosine 2 5 -diphosphate, and 6,2 -anhydro-1 - 3-D-arabinofuranosyl-6-hydroxycytosine. Adenosine 5 -triphosphate disodium salt, adenosine 5 -methylphosphate, adenosine 5-methylphosphonate, 8-methyladenosine 3-phosphate, 2-aza-adenosine, 9-ce-D-arabinofuranosyladenine, 8,2 -anhydro-9- 3-D-arabino-... 

Wittig methylenation of 3,5-di-0-benzyl-2-deoxy-D-erythrofuranose then reaction with MCPBA-boron trifluoride etherate afford 2,5-anhydro-4,6-di-0-benzyl-3-deoxy-D-ribohexitol. Mesylation of the latter followed by addition of the anion derived from adenine, furnished derivative 11. Cytidine and thymidine could be treated in a similar manner and de-O-benzylated by standard methods. Structures were verified by X-ray analysis. ... 

Uracil and cytosine derivatives of 4-thio-DL-erythrofuranose and adenine and guanine nucleoside analogues of 4-thio-D-ribofuranose, 4-thio-D-xylofuranose, and 5-thio-D-xylopyranose have been reported. Treatment of 2,2 -anhydro-cytosine with phosphorus pentasulphide gave the cyclic thiophosphate derivatives (49), which was used to prepare other 2 -thio-cytidine derivatives. The... 

Cyclocondensation of cytidine with acetylsalicyloyl chloride gave the corresponding 2,2 -anhydro-D"arabinofuranosyl-nucleoside, which was hydrolysed to give ara6/ o-cytidine. ... 

Cytidine has been converted into l-(5-amino-5-deoxy-j8-D-arabinofuranosyl) cytosine by a sequence of reactions involving A-benzoylation, sulphonation, acetylation, displacement with azide ion, e/c., and l-(3-amino-3-deoxy-jS-D-arabinofuranosyl)-6-azauracil was derived from 2, 3 -di-0-methanesulphonyl-5 -O-trityl-6-azauridine via 2,2 - and 2, 3 -anhydro-nucleosides. Other syntheses have been accomplished by the condensation of an appropriately derivatized amino-sugar with either a pyrimidine or purine derivative for example, the Hilbert route was used to prepare l-(2-amino-2-deoxy-a-D-arabino- and -jS-o-xylo-furanosyl)cytosine. > The reactivity of l,3,4,6-tetra-0-acetyl-2-acyl-amido-2-deoxy-j3-D-glucopyranoses in condensation reactions with 2,6-dichloro-purine, theophylline, and 6-benzylaminopurine was shown to be in the order benzamido > acetamido > phthalimido. 9-(3-Acetamido-2,5-di-0-acetyl-3-deoxy-j8-D-ribofuranosyl)-2,6-dichloropurine has been synthesized and converted into the corresponding 2,6-diamino- and 6-amino-2-chloro(fluoro)-nucleosides. ... 

Nudeosides, Nudeotides, and their Derivatives.—Uridine, uridine 5 -(niethyl oxyacetate), 6-chloro-9-j8-D-ribofuranosylpurine, 6-methyl-9-j8-D-ribofurano-sylpurine, 5-acetyl-l-(3,5-0-isopropylidene-j8-D-xylofuranosyl)uracil, 2 -de-oxycytidine, the 1 1-complex of cytidine and iV-benzyloxycarbonylglutamic acid, l-(3-0-methyl-j8-D-arabinofuranosyl)cytosine, 2 -deoxyadenosine 5 -(sodium phosphate), 9-j8-D-arabinofuranosyladenine hydrochloride, 8-j8-D-ribofuranosyladenine, 8 - (2 - deoxy - oc - d - erythro - pentofuranosyl) - 6 -hydroxy-purine, l-methyl-4-jS-D-erythrofuranosyl-4-imida2oline-2-thione, and 4,6-di-0-acetyl-l,3 -anhydro-2,3-dideoxy-3-[3-hydroxy-5-methyl-(2if)-l,2,6-thiadiazin-2-yl l,l-dioxide]-a-D-n 6o-hexopyranose (455). ... 

A series of three papers has described the reactions of 2-acyloxyisobutyryl chlorides with nucleosides (particularly cytidine) to give 3 - and 3, 5 -acylated 2,2 -anhydro-jS-D-arabinofuranosyl-nucleosides, which can be converted into the corresponding l-/3-D-arabinofuranosyl-nucleotides with either aqueous pyridine or sodium carbonate-sodium hydrogen carbonate in aqueous /j-dioxan. 2,2 -Anhydro-5-chloro-l-(5-chloro-5-deoxy-jS-D-arabinofuranosyl)cytosine was obtained on treatment of cytidine with sulphuryl chloride in acetonitrile similarly, 1- -D-arabinofuranosylcytosinegave2,2 -anhydro-5-chloro-l-(5-chloro-5-deoxy-j3-D-... 

The rate of formation of 6,2 -anhydro-3-D-arabino-, 6,3 -anhydro-g-D-xylo-, and 6,5 -anhydro-3-D-ribo-furanosyluridines, (11)-(13) respectively, on treatment of the corresponding 5-iodouracil nucleosides with sodium methoxide has been found to be in the order of (11)>>(12)>(13), corresponding to the ease of formation of 5,6 and 7-membered rings, respectively. The ease of acid hydrolysis was in the reverse order. The same relative ease of cycliz-ation has been observed with the cytidine nucleoside analogues. 

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