Collect. Czech. Chem. Commun. 1979, 44, 792-798

Synthesis of phosphoramidate analogs of ribodinucleoside phosphates

Alexei V. Azhayeva, Alexander A. Krayevskya and Jiří Smrtb

a Institute of Molecular Biology, USSR Academy of Sciences, Moscow, 117 312 U.S.S.R.
b Institute of Organic Chemistry and Biochemistry, Czechoslovak Academy of Sciences, 166 10 Prague 6


Cytidine 5'-phosphate (Ia) reacts with 1,1'-carbonyldiimidazole under the formation of 2',3'-O-carbonylcytidine 5'-phosphorimidazolidate (IIa) which affords (by the action of 3'-amino-3'-deoxyadenosine (IIIa)) 3'-deoxyadenosine-3'-amidophosphoryl-(3' → 5')-cytidine (IVa) and (by the action of 3'-amino-3-deoxy-N6-dimethyladenosine (IIIc)) 3'-deoxy-N6-dimethyladenosine-3'-amidophosphoryl-(3' → 5')-cytidine (IVc). Starting from adenosine 5'-phosphate (Ib) and 3'-amino-3'-deoxycytidine (IIIb) or the substance IIIc, 3'-deoxycytidine-3'-amidophosphoryl-(3' → 5')-adenosine (IVb) or 3'-deoxy-N6-dimethyladenosine-3'-amidophosphoryl-(3' → 5')-adenosine (IVd) were prepared. 6-Azauridine (V) was transformed, by the action of triphenylphosphine, lithium azide and carbon tetrabromide, followed by the action of triphenylphosphine and ammonia, to 5'-amino-5'-deoxy-6-azauridine (VI). The substance VI was transformed by the action of 2',3'-O-carbonyl-adenosine 5'-phosphorimidazolidate (IIb), to adenylyl-(5' → 5')-5'-amino-5'-deoxy-6-azauridine (VII). The compound IVb is not degraded by snake venom and spleen phosphodiesterases and is degraded by pancreatic ribonuclease to adenosine and the compound IIIb. The compound VII is degraded by snake venom phosphodiesterase to adenosine and the compound VI.