MILD PREPARATION OF PROTECTED PHOSPHATE-ESTERS FROM ALCOHOLS
MILD PREPARATION OF PROTECTED PHOSPHATE-ESTERS FROM ALCOHOLS
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DOI：
10.1021/jo00117a018
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发表时间：
1995-06-16
影响因子：
3.6
通讯作者：
CORCORAN, RC
中科院分区：
文献类型：
--
作者：
OZA, VB;CORCORAN, RC
用亚磷酸三甲酯和四溴化碳在吡啶中处理多种醇，可以高产率地生成相应的磷酸二甲酯。据推测，该反应是通过生成中间体烷氧基三甲氧基膦盐进行的，该盐经过溴化物的选择性脱甲基化。如果使用吡啶以外的溶剂，或者用四氯化碳代替四溴化碳，通常会得到较低的产率。高酸敏的2-(4，4‘-二甲氧基三甲氧基)-1-苯乙醇转化为其磷酸二甲酯(74%)，碱敏感的N-CBZ-酪氨酸对硝基苯酯转化为相应的O-(二甲基磷酸酯)(82%)，说明了该方法的温和。磷酸甲酯脱甲基化方法的出现使氧化磷酸化反应成为合成受保护的磷酸酯的一种温和而廉价的方法。
Treatment of a wide variety of alcohols with trimethyl phosphite and carbon tetrabromide in pyridine leads to the formation of the corresponding dimethyl phosphate esters in high yields. The reaction is presumed to proceed by formation of an intermediate alkoxy trimethoxyphosphonium salt which undergoes selective demethylation by bromide. Poor yields are generally obtained if solvents other than pyridine are employed or if carbon tetrabromide is replaced by carbon tetrachloride. The mildness of the procedure is illustrated by the conversion of the highly acid sensitive 2-(4,4'-dimethoxytrityloxy)-1-phenylethanol to its dimethyl phosphate ester (74%) and the base sensitive N-CBZ-tyrosine-p-nitrophenyl ester to the corresponding O-(dimethyl phosphate ester) (82%). The availability of methods for the demethylation of methyl phosphate esters makes this oxidative phosphorylation reaction a mild and inexpensive method for the synthesis of protected phosphate esters.