STEREOSPECIFIC CONTROL OF THE CITRATE SYNTHASE MEDIATED SYNTHESIS OF (2R,3R)-3-FLUOROCITRATE BY THE RELATIVE STABILITIES OF THE INTERMEDIATE FLUOROENOLATES
STEREOSPECIFIC CONTROL OF THE CITRATE SYNTHASE MEDIATED SYNTHESIS OF (2R,3R)-3-FLUOROCITRATE BY THE RELATIVE STABILITIES OF THE INTERMEDIATE FLUOROENOLATES
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DOI：
10.1039/c39940002029
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发表时间：
1994-09-21
影响因子：
--
通讯作者：
RZEPA, HS
中科院分区：
文献类型：
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作者：
OHAGAN, D;RZEPA, HS
通过从头算计算了氟硫酰基烯醇和烯醇酸酯的E-和Z-异构体的相对稳定性，提出了一个涉及氟乙酰-辅酶A的酶促缩合的立体化学过程的模型，其中我们认为，对于柠檬酸合成酶，烯醇中间体基本上是质子化的，而对于苹果酸合成酶则不是。
A model for the stereochemical course of enzymatically mediated condensations involving fluoroacetyl-CoA is provided by ab initio calculations of the relative stabilities of the E- and Z-isomers of fluorothioacyl enols and enolates, in which we suggest the enolate intermediate is substantially protonated for citrate synthase but not for malate synthase.