Mechanism and rate constant of proline-catalysed asymmetric aldol reaction of acetone and p-nitrobenzaldehyde in solution medium: Density-functional theory computation.
Mechanism and rate constant of proline-catalysed asymmetric aldol reaction of acetone and p-nitrobenzaldehyde in solution medium: Density-functional theory computation.
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DOI：
10.1016/j.jare.2018.03.002
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发表时间：
2018-07
影响因子：
10.7
通讯作者：
Abechi SE
中科院分区：
文献类型：
--
作者：
Tafida UI;Uzairu A;Abechi SE
为了寻求改进催化剂设计的新途径，目前的研究主要集中在利用量子力学描述符研究脯氨酸作为催化剂对不对称Aldol反应机理和速率的影响。采用密度泛函理论（DFT）方法，在6- 31 G DFT/B3 LYP水平上计算了丙酮和对硝基苯甲醛在丙酮介质中的最高占据分子轨道（HOMO）和最低未占分子轨道（LUMO）能量，并对反应机理进行了探讨.提出了新的机械步骤，并发现以下，与扩展，以前报道的亚胺-烯胺路线的典型的1类醛缩酶。从基本步骤中，第一步涉及丙酮和脯氨酸的双分子碰撞，被认为是速率决定步骤，具有最高的活化能59.07 kJ mol−1。该机制被用来开发的总速率常数计算和发现的速率定律。新的机理的见解和明确的计算速率常数进一步提高了动力学知识的反应。
In search of new ways to improve catalyst design, the current research focused on using quantum mechanical descriptors to investigate the effect of proline as a catalyst for mechanism and rate of asymmetric aldol reaction. A plausible mechanism of reaction between acetone and 4-nitrobenzaldehyde in acetone medium was developed using highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies calculated via density functional theory (DFT) at the 6-31G∗/B3LYP level of theory. New mechanistic steps were proposed and found to follow, with expansion, the previously reported iminium-enamine route of typical class 1 aldolase enzymes. From the elementary steps, the first step which involves a bimolecular collision of acetone and proline was considered as the rate-determining step, having the highest activation energy of 59.07 kJ mol−1. The mechanism was used to develop the rate law from which the overall rate constant was calculated and found to be . The new mechanistic insights and the explicit computation of the rate constant further improve the kinetic knowledge of the reaction.
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影响因子：
15
作者：
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通讯作者：
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