Nucleoside und Nucleotide. Teil 15. Synthese von Desoxyribonucleosid‐monophosphaten und ‐triphosphaten mit 2(1H)‐Pyrimidinon, 2(1H)‐Pyridinon und 4‐Amino‐2(1H)‐pyridinon als Basen

Nucleosides and Nucleotide. Part 15. Synthesis of Deoxyribonucleoside Monophosphates and Triphosphates with 2(1H)‐Pyrimidinone, 2(1H)‐Pyridinone and 4‐Amino‐2(1H)‐pyridinone as the Bases The phosphorylation of the modified nucleosides 1‐(2′‐deoxy‐β‐D‐ribofuranosyl)‐2(1 H)‐pyrimidinone (Md, 4), 4‐amino‐1‐(2′‐deoxy‐β‐D‐ribofuranosyl)‐2(1 H)‐pyridinone (Zd, 6) and the synthesis of 1–2′‐deoxy‐β‐D‐ribofuranosyl‐2(1 H)‐pyrimidinone‐5′‐O‐triphosphate (pppMd, 1), 1‐(2′‐deoxy‐β‐Dribofuranosyl)‐2(1 H)‐pyridinone‐5′‐O‐triphosphate (pppIId, 2), and 4‐amino‐1‐(2′‐deoxy‐βD‐ribofuranosyl)‐2(1 H)‐pyridinone‐5′‐O‐triphosphate (pppZd, 3) are described. The nucleoside‐5′‐monophosphates pMd (5) and pZd (7) were obtained by selective phosphorylation of Md (4) and Zd (6), respectively, using phosphorylchloride in triethyl phosphate or in acetonitril. The reaction of pMd (5) pII d (8) or pZd (7) with morpholine in the presence of DCC led to the phosphoric amides 9, 10 and 11, respectively, which were converted with tributylammonium pyrophosphate in dried dimethylsulfoxide to the nucleoside‐5′triphosphates 1, 2 and 3, respectively.