Peliska J A, O'Leary M H
Department of Chemistry, University of Wisconsin-Madison 53706.
Biochemistry. 1989 Feb 21;28(4):1604-11. doi: 10.1021/bi00430a027.
Sulfoenolpyruvate, the analogue of phosphoenolpyruvate in which the phosphate ester has been replaced by a sulfate ester, has been synthesized in three chemical steps from ethyl bromopyruvate in 40% overall yield. This compound is a substrate for pyruvate kinase, producing pyruvate and adenosine 5'-sulfatopyrophosphate. The latter compound has been identified by NMR spectroscopy and by comparison with an authentic sample. Sulfuryl transfer from sulfoenolpyruvate is 250-600-fold slower than phosphate transfer from phosphoenolpyruvate under identical conditions. Sulfoenolpyruvate is not a substrate for phosphoenolpyruvate carboxylase. Kinetic studies reveal that it does not bind to the active site; instead, it binds to the site normally occupied by glucose 6-phosphate and activates the enzyme in a manner similar to that shown by glucose 6-phosphate.
磺基烯醇丙酮酸是磷酸烯醇丙酮酸的类似物，其中磷酸酯被硫酸酯取代，它由溴丙酮酸乙酯经三步化学合成，总产率为40%。该化合物是丙酮酸激酶的底物，可生成丙酮酸和5'-腺苷硫酸焦磷酸。后一种化合物已通过核磁共振光谱并与标准样品比较进行了鉴定。在相同条件下，磺基烯醇丙酮酸的硫酰基转移比磷酸烯醇丙酮酸的磷酸转移慢250 - 600倍。磺基烯醇丙酮酸不是磷酸烯醇丙酮酸羧化酶的底物。动力学研究表明它不与活性位点结合；相反，它与通常由6-磷酸葡萄糖占据的位点结合，并以类似于6-磷酸葡萄糖的方式激活该酶。
