AQUEOUS ACCELERATION OF THE CLAISEN REARRANGEMENT OF ALLYL VINYL ETHER - A HYBRID, EXPLICIT SOLVENT, AND CONTINUUM MODEL
AQUEOUS ACCELERATION OF THE CLAISEN REARRANGEMENT OF ALLYL VINYL ETHER - A HYBRID, EXPLICIT SOLVENT, AND CONTINUUM MODEL
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DOI：
10.1021/j100017a067
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发表时间：
1995-04-27
影响因子：
--
通讯作者：
HILLIER, IH
中科院分区：
文献类型：
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作者：
DAVIDSON, MM;HILLIER, IH
描述了基于可极化连续介质模型的溶剂化模型，包括显式水分子和剩余溶剂的描述，并用于研究在水介质中观察到的烯丙基乙烯基醚克莱森重排的加速。从头算 HF/6-31G* 和 MP2 水平的计算表明，溶剂的主要影响是通过显式水分子有效模拟的。该模型产生的势垒降低与实验非常一致。我们的处理预测的由水合引起的动力学同位素效应的变化与实验建议的有些不同。
A model of solvation, including both explicit water molecules and a description of the remaining solvent, based upon the polarizable continuum model is described and used to study the acceleration of the Claisen rearrangement of allyl vinyl ether observed in aqueous medium. The calculations, at the ab initio HF/6-31G* and MP2 levels, show that the major effect of the solvent is effectively modelled by the explicit water molecules. This model yields a barrier lowering in excellent agreement with experiment. The changes in the kinetic isotope effects arising from hydration, predicted by our treatment, differ somewhat from those suggested by experiment.