（E）-3-氰基磷酸烯醇丙酮酸，一种磷酸烯醇丙酮酸依赖性酶的新型抑制剂。
(E)-3-Cyanophosphoenolpyruvate, a new inhibitor of phosphoenolpyruvate-dependent enzymes.
作者信息
Wirsching P, O'Leary M H
出版信息
Biochemistry. 1985 Dec 17;24(26):7602-6. doi: 10.1021/bi00347a015.
(E)-3-Cyanophosphoenolpyruvate has been synthesized by reacting dimethyl chlorophosphate with the potassium enolate of ethyl cyanopyruvate. The resulting trialkyl ester was deesterified with bromotrimethylsilane followed by potassium hydroxide. Subsequent treatment with Dowex-50-H+ resin and cyclohexylamine afforded the tricyclohexylammonium salt; only the E geometric isomer was obtained. This compound can be photoisomerized to a 70:30 E:Z mixture. (E)-3-Cyanophosphoenolpyruvate is an excellent competitive inhibitor of phosphoenolpyruvate carboxylase [KI(Mn2+) = 16 microM, KI(Mg2+) = 1360 microM], pyruvate kinase [KI(Mn2+) = 0.085 microM, KI(Mg2+) = 0.76 microM], and enolase [KI(Mn2+) = 360 microM, KI(Mg2+) = 280 microM]. The compound is a substrate for pyruvate kinase (Vmax approximately 1% of phosphoenolpyruvate rate), but not for the other two enzymes. No irreversible inactivation is observed with phosphoenolpyruvate carboxylase of pyruvate kinase.
通过使氯磷酸二甲酯与氰基丙酮酸乙酯的烯醇钾反应合成了(E)-3-氰基磷酸烯醇丙酮酸。所得的三烷基酯先用溴化三甲基硅烷进行脱酯反应，然后用氢氧化钾处理。随后用Dowex-50-H+树脂和环己胺处理得到三环己基铵盐；仅得到E型几何异构体。该化合物可通过光异构化为70:30的E:Z混合物。(E)-3-氰基磷酸烯醇丙酮酸是磷酸烯醇丙酮酸羧化酶[KI(Mn2+) = 16 microM，KI(Mg2+) = 1360 microM]、丙酮酸激酶[KI(Mn2+) = 0.085 microM，KI(Mg2+) = 0.76 microM]和烯醇酶[KI(Mn2+) = 360 microM，KI(Mg2+) = 280 microM]的优良竞争性抑制剂。该化合物是丙酮酸激酶的底物（Vmax约为磷酸烯醇丙酮酸速率的1%），但不是另外两种酶的底物。磷酸烯醇丙酮酸羧化酶或丙酮酸激酶未观察到不可逆失活。
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