Neighboring Group Participation in Phosphate Ester Hydrolysis
Neighboring Group Participation in Phosphate Ester Hydrolysis
复制标题
邻近基团参与磷酸酯水解
DOI：
10.1021/ja00905a043
复制
发表时间：
1963
影响因子：
15
通讯作者：
A. Kirby
中科院分区：
文献类型：
--
作者：
V. M. Clark;A. Kirby
IV (R= CH3) 的甲基的水解比在酸性条件下用简单的磷酸二烷基酯观察到的水解要快得多。 5 此外，在产品的烯醇酯键发生可检测到的水解之前，该过程就已完成。这些观察结果表明，在类似条件下，磷酸单烷基酯和磷酸二烷基酯的相对反应性的通常顺序发生了逆转，6·6，即使在这种情况下单酯是烯醇磷酸酯。我们建议邻近的羧基参与水解。 7 一种可能的机制涉及羧酸氧对磷的亲核攻击。 ch2 ch20 c
The hydrolysis of the methyl group of IV (R= CH3) is much faster than that observed with simple dialkyl phosphates under acidic conditions. 5 More-over, it is complete before detectable hydrolysis of the enol-ester linkage of the product occurs. These observations indicate a reversal of the usual order of relative reactivity of the mono- and dialkyl phosphates under similar conditions, 6· 6 even though in this case the monoester is an enol phosphate. We suggest that the neighboring carboxyl group participates in the hydrol-ysis. 7 One possible mechanism involves nucleophilic attack on phosphorus by carboxylate oxygen. ch2 ch20 c