Solvation Effects on Claisen Rearrangement Investigated by QM/MM MD
作者单位：College of Chemistry and Molecular EngineeringPeking University
会议名称：《中国化学会第十二届全国量子化学会议》
会议日期：2014年
学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学]
摘 要：QM/MM hybrid molecular simulations of aliphatic Claisen rearrangement in several solvents have been *** adopting a highly efficient sampling method,SITS,an unreported but not unexpected result was observed that the reactant underwent a conformational pre-adjustment before it arrived at the transition *** to this outcome in addition to the echo from the structure of natural enzyme,a two-step process of Claisen rearrangement has been proposed,which consists of the necessary trapping into a favorable compact conformation and the subsequent reorganization of chemical bonds and *** to the post-simulation analysis,solvents with high CED were able to accommodate compact conformers *** were found to be partially polarized during the conformational transitions in solvents like water and ionic *** different substituents would shift the conformational ***,by virtue of the enhanced sampling of reactive trajectories（ESo RT）,the rate constant of electron rearrangement of parent AVE in water has been statistically calculated,which was about hundreds of times faster than that in benzene or di-（n）butyl *** result was in line with the experimental measurement and provided more insight to the well-known but mysteriousin/on waterfacilitation effect.