Shinozuka K, Matsumoto N, Nakamura A, Hayashi H, Sawai H
Faculty of Engineering, Gunma University, 1-5-1 Tenjincho, Kiryu, Gunma 376-8515, Japan.
Nucleic Acids Symp Ser. 2000(44):21-2. doi: 10.1093/nass/44.1.21.
A facile stereospecific synthetic method for alpha-anomeric 2'-deoxypyrimidine nucleoside unit utilizing aminooxazoline derivative of ribofuranose was investigated. Thus, easily accessible riboaminooxazoline derivative prepared by ribose and cyanamid was allowed to react with ethyl alpha-bromoethylacrylate to give corresponding adduct. The adduct was cyclized by strong base such as potassium t-butokiside. The resulted 2,2'-cyclonucleoside was then treated with acetyl bromide followed by n-butyltin hydride to give alpha-anomeric 3',5'-di-O-acetylthymidine. 3',5'-Di-O-acety groups of the nucleoside were easily removed by the action of excess of triethyl amine in methanol. Essentially same procedure afforded corresponding 2'-deoxyuridine, which was further, converted to alpha-anomeric 2'-deoxycytidine.
研究了一种利用呋喃核糖的氨基恶唑啉衍生物合成α-异头2'-脱氧嘧啶核苷单元的简便立体定向合成方法。因此，由核糖和氰胺制备的易于获得的核糖氨基恶唑啉衍生物与α-溴代丙烯酸乙酯反应得到相应的加合物。该加合物用强碱如叔丁醇钾环化。然后将所得的2,2'-环核苷用乙酰溴处理，接着用正丁基氢化锡处理，得到α-异头3',5'-二-O-乙酰胸苷。核苷的3',5'-二-O-乙酰基通过在甲醇中过量三乙胺的作用很容易除去。基本上相同的步骤得到相应的2'-脱氧尿苷，其进一步转化为α-异头2'-脱氧胞苷。
