Wirsching P, O'Leary M H
Department of Chemistry, University of Wisconsin--Madison 53706.
Biochemistry. 1988 Feb 23;27(4):1355-60. doi: 10.1021/bi00404a040.
1-Carboxyallenyl phosphate, the allenic homologue of phosphoenolpyruvate, has been synthesized in six steps. The key step in the synthesis is the isomerization of methyl 2-hydroxy-3-butynoate to the corresponding allenol and phosphorylation of this material. The allene is an excellent substrate for pyruvate kinase, undergoing reaction at more than half the rate of phosphoenolpyruvate. The allene is also a substrate for phosphoenolpyruvate carboxylase, being hydrolyzed by the enzyme rather than carboxylated. With both enzymes, the organic product is 2-oxo-3-butenoate, which gradually inactivates the enzymes by reaction with one or more sulfhydryl groups not at the active site.
磷酸1-羧基丙二烯酯，即磷酸烯醇丙酮酸的丙二烯同系物，已通过六步合成出来。合成中的关键步骤是将2-羟基-3-丁炔酸甲酯异构化为相应的丙二烯醇并对该物质进行磷酸化。丙二烯是丙酮酸激酶的优良底物，其反应速率超过磷酸烯醇丙酮酸的一半。丙二烯也是磷酸烯醇丙酮酸羧化酶的底物，被该酶水解而非羧化。对于这两种酶而言，有机产物都是2-氧代-3-丁烯酸酯，它通过与一个或多个不在活性位点的巯基反应而逐渐使酶失活。
