Adenosine 3 -deoxy-, synthesis

Martarello L, Schaffrath C, Deng H, Gee AD, Lockhart A, O Hagan D (2003) The First Enzymatic Method for C-18F Bond Formation The Synthesis of 5 -[18F]-Fluoro-5 -deoxy-adenosine for Imaging with PET. J Label Compd Radiopharm 46 1181... 

A potent blocker. How does cordycepin (3 -deoxy adenosine) block the synthesis of RNA ... 

Benhida described the synthesis of a 2-deoxy-C-nucleoside analogue and its phosphoramidite derivative featuring 6-(thiazolyl-5)-a-benzimidazole nucleobase (134). A more efficient route to the expanded adenosine analogue (135) was developed by Kool, who also described the synthesis of the expanded thymidine analogue (136) starting from 5-methylanthranilic acid. Both nucleosides were found to be efficient fluorophores. 3 -Cyanoethyl phosphoramidites of 6-methyl-3-(2 -deoxy-(3-D-ribofuranosyl)-3//-pyrrolo[2,3-d]pyrimidin-2-one... 

The synthesis and incorporation into oligonucleotides of the A-phosphory-lated deoxycytidine 3 -phosphoramidites (144) and (145) obtained either from the O-protected 2 -deoxycytidine and bis(2-cyanoethyl) A,A-diisopropyl phosphoramidite or diethylphosphorochloridite, respectively, was described by Sekine. Sekine also reported that the A-phosphorylated derivatives of 2 -deoxy adenosine decomposed readily and were unsuitable for incorporation into oligodeoxynucleotides. 

The first synthesis of FddA (1) from 3 -deoxy adenosine derivative by Herdewijn et al. gave the fluorination product in only 10% overall yield after deprotection and purification [59]. Several years later, we also examined a similar reaction with the 5 -O-acetyl compound, but the yield was confirmed to be very poor [71]. We hypothesized that one possible reason for the low fluorination yield in the above reaction might be the nucleophilic participation of N-3 of the adenine ring, and that this might be overcome by using 6-chloropurine 3 -deoxyriboside as a starting material (see also Section 7.3.1.2.1). 

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