腺嘌呤核苷3′,5′-环烷基膦酸类似物的立体化学研究

Studies on Stereochemistry of Adenosine 3' , 5'-Cycloalkylphosphonate

利用一维NOE差谱技术确定了2′-对甲苯磺酰基-腺嘌呤核苷3′,5′-环甲基和环正丁基膦酸类似物磷原子的绝对构型。二维(J,δ)分解谱分析表明,它们的膦酸环的构象为椅式和扭船式并存,以椅式为主,扭船式构象的分数随溶剂极性的增加或随温度的升高而增加;它们的碱性水解开环产物以磷原子连在5′-OH为主。

The configuration of phosphorus in 2'-toluenesulfonyl-adenosine-;3' ,5,'-cydlc methyl phos-phonate (Ⅰ) and cyciic-R-butylphosphonate ( Ⅰ ) were determined by using NOE technique, The data indicate that they are S forms. The conformations of cyeloalkylphosphonate moieties were identified by two dimension HOM2DJ spectroscopy which shows that there exists an equilibrium between chair and twist forms in the solution. The population of chair conformation is higher than that of twist conformation and the ratio increased with increase of the polarity of solvent and temperature. The main hydrolysates of Ⅰ and Ⅱ in NH4OH and CH3OH are derivatives of nucleoside 5'-alkylphosphonate.