Studies of Phosphorylation. III. Selective Phosphorylation of Unprotected Nucleosides
Studies of Phosphorylation. III. Selective Phosphorylation of Unprotected Nucleosides
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磷酸化的研究。
DOI：
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发表时间：
1969
期刊：
影响因子：
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通讯作者：
T. Takenishi
中科院分区：
文献类型：
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作者：
M. Yoshikawa;Tetsuya Kato;T. Takenishi
在考察了影响2‘，3’-O-异丙叉核苷与磷酰氯反应的因素时，发现三烷基磷酸盐是磷酸化反应的有力促进剂和有用的溶剂。在大量磷酰氯的基础上加入三烷基磷酸酯，可以有效地促进磷酸化；此外，低烷基磷酸盐，如三甲基和三乙基磷酸盐，能够取代过量的磷酰氯作为溶剂。未保护的核苷在磷酸三甲酯中用磷酰氯处理时，主要生成相应的5‘-磷酸，同时还有少量高度磷酸化的产物，产率较高。相反，5‘-O-乙酰基核苷以类似的方式处理，以低产率得到相应的2’(或3‘)-核苷酸。在反应混合物中加入少量水可强烈抑制2‘(或3’)-磷酸的生成。这..。
During an investigation of the factors affecting the reaction of 2′,3′-O-isopropylidene nucleosides with phosphoryl chloride, trialkyl phosphates were found to be powerful accelerators and useful solvents for the phosphorylation. The addition of a trialkyl phosphate to a large excess of phosphoryl chloride was markedly effective in promoting the phosphorylation; further, the lower alkyl phosphates, such as trimethyl and triethyl phosphates, were able to replace the excessive amount of phosphoryl chloride as solvents. When unprotected nucleosides were treated with phosphoryl chloride in trimethyl phosphate, the corresponding 5′-phosphates were mainly produced, together with a small amount of highly-phosphorylated products, in good yields. On the contrary, the treatment of 5′-O-acetyl nucleosides in a similar manner gave the corresponding 2′(or 3′)-nucleotides in low yields. The formation of the 2′(or 3′)-phosphate was strongly inhibited by the addition of a small amount of water to the reaction mixture. Th...