文献类型：期刊文献

英文题名：Mechanism and reactivity in the Morita-Baylis-Hillman reaction: the challenge of accurate computations

作者：Liu, Zhen[1,2];Patel, Chandan[3];Harvey, Jeremy N.[1];Sunoj, Raghavan B.[3]

机构：[1]Katholieke Univ Leuven, Dept Chem, Celestijnenlaan 200F, B-3001 Leuven, Belgium;[2]East China Univ Sci & Technol, State Key Lab Chem Engn, Meilong Rd 130, Shanghai 200237, Peoples R China;[3]Indian Inst Technol, Dept Chem, Bombay 400076, Maharashtra, India

年份：2017

卷号：19

期号：45

起止页码：30647

外文期刊名：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000416054400035)】；

基金：This work received support from the KU Leuven grant #C14/15/052, and from the Office of China Postdoctoral Council (no. 20140061) through the International Postdoctoral Exchange Fellowship Program. We acknowledge the Flemish Supercomputer Centre (VSC), the supercomputer at ECUST Shanghai, and the SpaceTime supercomputing facility at IIT Bombay for generous computing resources.

语种：英文

摘要：A systematic density functional theory exploration of various reactive steps together with benchmark coupled cluster results are used to propose an accurate model of the mechanism of the Morita-Baylis-Hillman (MBH) reaction in organic chemistry. This reaction has attracted considerable interest from the synthetic and mechanistic points of view in recent years, with both computational and experimental mechanistic studies. It has recently (R. E. Plata and D. A. Singleton, J. Am. Chem. Soc., 2015, 137, 3811-3826) been correctly pointed out that previous computational studies failed to reproduce known mechanistic features of the reaction. The same study argued that computation is simply not able at the present time to provide accurate models for such reactions. This second claim is shown by our present work to overstate the problem: by using current 'state of the art' methodology, our results are fully consistent with observed behavior within the expected error bars of 1-5 kcal mol(-1), far smaller than the errors reported in Plata and Singleton's study. On the basis of exhaustive calculations reported here, we suggest that our proposed approaches for modeling electronic structure, solvation, and entropy should be able to provide accurate predictions for many more reactions. We also suggest that reactions like the MBH reaction, where solvation and entropy effects are particularly large, are among the hardest for computational mechanistic studies.