Computer-assisted study on the reaction between pyruvate and ylide in the pathway leading to lactyl-ThDP
Computer-assisted study on the reaction between pyruvate and ylide in the pathway leading to lactyl-ThDP
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DOI：
10.1007/s10822-012-9589-3
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发表时间：
2012-08-01
影响因子：
3.5
通讯作者：
Delgado, Eduardo J.
中科院分区：
文献类型：
--
作者：
Alvarado, Omar;Jana, Gonzalo;Delgado, Eduardo J.
本文采用密度泛函理论（DFT）在X3 LYP/6-31++G（d，p）水平上研究了乳酰硫胺素二磷酸中间体（L-ThDP）的形成过程.该研究包括势能面扫描、过渡态搜索和内禀反应坐标计算。根据福井函数分析反应性。结果允许得出结论，导致形成L-ThDP的反应通过协调机制发生，并且在丙酮酸分子上的亲核攻击期间，叶立德处于其AP形式。计算的反应活化能为19.2千卡/摩尔，与实验报道的值一致。
In this study the formation of the lactyl-thiamin diphosphate intermediate (L-ThDP) is addressed using density functional theory calculations at X3LYP/6-31++G(d,p) level of theory. The study includes potential energy surface scans, transition state search, and intrinsic reaction coordinate calculations. Reactivity is analyzed in terms of Fukui functions. The results allow to conclude that the reaction leading to the formation of L-ThDP occurs via a concerted mechanism, and during the nucleophilic attack on the pyruvate molecule, the ylide is in its AP form. The calculated activation barrier for the reaction is 19.2 kcal/mol, in agreement with the experimental reported value.