SYNTHESIS OF NUCLEOSIDES .9. GENERAL SYNTHESIS OF N-GLYCOSIDES .1. SYNTHESIS OF PYRIMIDINE NUCLEOSIDES
SYNTHESIS OF NUCLEOSIDES .9. GENERAL SYNTHESIS OF N-GLYCOSIDES .1. SYNTHESIS OF PYRIMIDINE NUCLEOSIDES
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DOI：
10.1021/jo00939a008
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发表时间：
1974-01-01
影响因子：
3.6
通讯作者：
VORBRUGGEN, H
中科院分区：
文献类型：
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作者：
NIEDBALLA, U;VORBRUGGEN, H
14，以甲硅烷基化的5-乙基尿嘧啶(5)为原料，在1,2-二氯乙烷中于22℃下20小时后得到95％。甲硅烷基化的 5-正丁基尿嘧啶 (7) 与 1, 2-二氯乙烷中的 2 反应非常缓慢，但在添加乙腈和额外量的 SnCl* 后，以 95% 的产率得到 5-正丁基尿苷 2,,3,, 5/-三-0-苯甲酸酯 (8) 16。然而，相应的甲硅烷基化的5-正丁基-2-硫尿嘧啶(9)在乙腈中5小时后得到2-硫代类似物1016b，产率83%。令人惊奇的是，甲硅烷基化的5-硝基尿嘧啶(11)的反应在22℃下在1,2-二氯乙烷-乙腈中在0.5小时内完成，得到5-硝基尿苷2,,3',5,-三-0-苯甲酸酯(12)，收率98％。全甲硅烷基化的2-硫胞嘧啶(13) 8 与2反应，以95%的收率得到2-硫胞苷2/,3/,5/-三-0-苯甲酸酯(14),8>17，其与甲醇氨以极好的收率得到2-硫胞苷，一种来自t-RNA的稀有核苷。 18 这些结果表明，在 SnCU 存在下，硅烷化碱基的结构与其在 1, 2-二氯乙烷和乙腈中的核苷形成速率之间存在复杂的关系（另请比较本系列的论文 II 和 IV）。
14, 95% after 20 hr at 22 in 1, 2-dichloroethane starting from sily-lated 5-ethyluracil (5). Silylated 5-n-butyluracil (7) reacted very slowly with 2 in 1, 2-dichloroethane, but gave 5-n-butyluridine 2,, 3,, 5/-tri-0-benzoate (8) 16 in 95% yield after addition of acetonitrile and an additional amount of SnCl*. The corresponding silylated 5-n-butyl-2-thiouracil (9), however, afforded the 2-thio analog 1016b after 5 hr in ace-tonitrile in 83% yield. Surprisingly the reaction of silylated 5-nitrouracil (11) was complete in 0.5 hr at 22 in 1, 2-dichloroethane—acetonitrile to give 5-nitrouridine 2,, 3', 5,-tri-0-benzoate (12) in 98% yield. Persilylated 2-thiocytosine (13) 8 reacted with 2 to afford in 95% yield 2-thiocytidine 2/, 3/, 5/-tri-0-benzoate (14), 8> 17 which gave with methanolicammonia in excellent yield 2-thiocytidine, a rare nucleoside from t-RNA. 18 These resultsindicate a complex relationship between the structure of the silylated bases and their rate of nucleoside formation in 1, 2-dichloroethane and acetonitrile in the presence of SnCU (compare also papers II and IV of this se-ries).