SYNTHESIS AND REACTIVITY OF 6-SUBSTITUTED (Z)-2-EN-4-YNOIC ACIDS
SYNTHESIS AND REACTIVITY OF 6-SUBSTITUTED (Z)-2-EN-4-YNOIC ACIDS
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DOI：
10.1021/jo00132a023
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发表时间：
1982-01-01
影响因子：
3.6
通讯作者：
SELTZER, S
中科院分区：
文献类型：
--
作者：
STRUVE, G;SELTZER, S
五种不同的6-取代(Z)-2-烯-4-乙烯酸（X = CH3, CH3CHOH, CH3C）。合成了CH2), CH3CHOAc, CH3CO)[马来丙酮顺反异构酶]。前3个是由甲基(Z)-3-碘丙烯酸酯与适当的乙酰亚铜偶联形成的，然后进行酯水解。后2种化合物分别由羟基化合物经乙酰化和氧化得到。5个化合物中的3个通过羧酸基团亲核加成到乙炔碳上，得到具有特定反式加成的4-烷基烯-2-丁烯内酯衍生物。标题化合物（X = CH3 CO）的内酯化速率太快，无法测量。测定了（X = CH3CHOAc和CH3CHOH）在水和二甲基甲酰胺中的内酯化动力学。观察到的内酯化速率比表明邻近的醋酸基团可能有亲电催化作用。
Five different 6-substituted (Z)-2-en-4-ynoic acids (X = CH3, CH3CHOH, CH3C(.dbd.CH2), CH3CHOAc, CH3CO) were synthesized [maleylacetone cis-trans isomerase]. The first 3 were formed by coupling of methyl (Z)-3-iodopropenoate and the appropriate cuprous acetylide followed by ester hydrolysis. The latter 2 were obtained from the hydroxyl compound by acetylation and oxidation, respectively. Three of the 5 compounds undergo lactonization by nucleophilic addition of the carboxylate group to the acetylenic carbon to yield 4-alkylidene-2-butenolide derivatives with specific trans addition. The rate of lactonization for the title compound (X = CH3 CO) is too fast to measure. The kinetics of lactonization for (X = CH3CHOAc and CH3CHOH were measured in water and dimethylformamide. The observed rate ratio for lactonization suggests the possibility of electrophilic catalysis by the neighboring acetate group.