Liu Min-Hsien, Tsai Hou-Jen, Liu Chuan-Wen
Department of Chemical and Materials Engineering, Chung Cheng Institute of Technology, National Defense University, Taoyuan, Republic of China.
J Mol Model. 2017 Aug;23(8):246. doi: 10.1007/s00894-017-3414-9. Epub 2017 Jul 28.
In respective water or ethanol polarizable continuum cavity environments, simultaneous aldol condensation was performed using density functional theory (DFT) computational method to model the synthesis of optically active (RS)-1,2,4-butanetriol trinitrate (BTTN). The results of reaction energy barrier analysis suggested feasible routes with lower activation energies to obtain either the (R)- or (S)-configuration product in ethanolic solution. In addition, local analysis of average inter-particulate distances of reaction species revealed that a stronger inter-particulate interaction accompanied a shorter average distance in the ethanol system. The stabilization effect also indicated that related syntheses would be able to proceed in ethanol. Furthermore, relative to the production of (R)-BTTN, a lower overall energy of 425.3 kJ/mol was required for the synthesis of (S)-BTTN. Through analysis of the effects of temperature on the reaction rates of individual parallel stages of (R)- and (S)-species synthesis, it was simple to adjust the reaction temperature accordingly to differentiate between relative rates in order to obtain a product of a specific configuration. Graphical abstract ᅟ.
在各自的水或乙醇可极化连续介质腔环境中，使用密度泛函理论（DFT）计算方法进行同时羟醛缩合反应，以模拟光学活性（RS）-1,2,4-丁三醇三硝酸酯（BTTN）的合成。反应能垒分析结果表明，在乙醇溶液中存在具有较低活化能的可行路线来获得（R）-或（S）-构型产物。此外，对反应物种平均颗粒间距离的局部分析表明，乙醇体系中颗粒间相互作用越强，平均距离越短。稳定化效应还表明相关合成反应能够在乙醇中进行。此外，相对于（R）-BTTN的生成，（S）-BTTN的合成所需的总能量更低，为425.3 kJ/mol。通过分析温度对（R）-和（S）-物种合成的各个平行阶段反应速率的影响，可以简单地相应调整反应温度以区分相对速率，从而获得特定构型的产物。图形摘要ᅟ。
