Godovikova T S, Zarytova V F, Mal'tseva T V, Khalimskaia L M
Bioorg Khim. 1989 Sep;15(9):1246-52.
Method of synthesis and isolation of oligonucleotide derivatives with a zwitterionic terminal phosphate group, containing N-methylimidazole (MeIm), 4-dimethylaminopyridine (DMAP) or 4-dimethylaminopyridine 1-oxide (DMAPO) residues has been developed. Mononucleotide derivatives were used to study the reactivity of these compounds to various nucleophiles and the dependence of hydrolysis rate on pH of solution. These compounds interact rapidly and quantitatively with aliphatic amines and much slower with water, aniline and methanol. MeIm derivatives are most active to nucleophiles, whereas the reactivity of DMAP derivatives is ca. 5 times lower and that of DMAPO derivatives is lower by 2 order of magnitude. This method of activating terminal phosphate group is promising for synthesis of various oligonucleotide phosphoramidates.
已开发出合成和分离具有两性离子末端磷酸基团、含有N-甲基咪唑（MeIm）、4-二甲基氨基吡啶（DMAP）或4-二甲基氨基吡啶1-氧化物（DMAPO）残基的寡核苷酸衍生物的方法。使用单核苷酸衍生物来研究这些化合物对各种亲核试剂的反应性以及水解速率对溶液pH值的依赖性。这些化合物与脂肪族胺快速定量相互作用，而与水、苯胺和甲醇的相互作用则慢得多。MeIm衍生物对亲核试剂最具活性，而DMAP衍生物的反应性约低5倍，DMAPO衍生物的反应性低2个数量级。这种活化末端磷酸基团的方法对于合成各种寡核苷酸亚磷酰胺酯具有前景。
