[Synthesis of 3'-deoxy-3'-carboxymethylnucleosides, precursors of oligonucleotides with an amide internucleoside bond].
An improved method for the synthesis of 3-deoxy-3-carboxymethylnucleosides was suggested. Oxidation of 5-O-benzoyl-l,2-O-isopropylidene-alpha-D-xylofuranose resulted in the 3-keto derivative, which was treated with triethylphosphonoacetate in the presence of sodium hydride to obtain the 3-deoxy-3-ethoxycarbonylmethylene derivative. Hydrogenation of the unsaturated compound proceeded strictly stereospecifically and gave the product with the ribo configuration. Acetolysis of the resulting compound with AcOH-Ac2O-CH3SO3H led to 1,2-di-O-acetyl-5-O-benzoyl-3-deoxy-3-ethoxycarbonylmethyl-D-ribofuranose, whose interaction with persilylated nucleic bases gave 3-deoxy-3-ethoxycarbonylmethylnucleosides in a total yield of 42-49% from the starting compound.
Kochetkova
S V
SV
Varizhuk
A M
AM
Kolganova
N A
NA
Timofeev
E N
EN
Florent'ev
V L
VL
D009705:Nucleosides / Q000138:chemical synthesis* / Q000737:chemistry; D009841:Oligonucleotides / Q000737:chemistry*; D013237:Stereoisomerism
D009705:Nucleosides; D009841:Oligonucleotides