离子对SN2取代反应：抗衡离子和溶剂效应的活化应变分析
Ion-Pair SN 2 Substitution: Activation Strain Analyses of Counter-Ion and Solvent Effects.
作者信息
Laloo Jalal Z A, Rhyman Lydia, Ramasami Ponnadurai, Bickelhaupt F Matthias, de Cózar Abel
机构信息
Computational Chemistry Group, Department of Chemistry, Faculty of Science, University of Mauritius, Réduit, 80837, Mauritius.
Department of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, P.O. Box 2457, Riyadh, 11451, Saudi Arabia.
出版信息
Chemistry. 2016 Mar 18;22(13):4431-9. doi: 10.1002/chem.201504456. Epub 2016 Feb 16.
The ion-pair SN 2 reactions of model systems MnF(n-1) +CH3Cl(M(+) =Li(+), Na(+), K(+), and MgCl(+); n=0, 1) have been quantum chemically explored by using DFT at the OLYP/6-31++G(d,p) level. The purpose of this study is threefold: 1) to elucidate how the counterion M(+) modifies ion-pair SN 2 reactivity relative to the parent reaction F(-) +CH3Cl; 2) to determine how this influences stereochemical competition between the backside and frontside attacks; and 3) to examine the effect of solvation on these ion-pair SN2 pathways. Trends in reactivity are analyzed and explained by using the activation strain model (ASM) of chemical reactivity. The ASM has been extended to treat reactivity in solution. These findings contribute to a more rational design of tailor-made substitution reactions.
通过在OLYP/6 - 31++G(d,p)水平上使用密度泛函理论（DFT）对模型体系MnF(n - 1)+CH3Cl（M(+) = Li(+)、Na(+)、K(+)和MgCl(+)；n = 0, 1）的离子对SN2反应进行了量子化学研究。本研究目的有三个：1）阐明抗衡离子M(+)相对于母体反应F(-)+CH3Cl如何改变离子对SN2反应活性；2）确定这如何影响背面和正面进攻之间的立体化学竞争；3）研究溶剂化对这些离子对SN2反应途径的影响。通过使用化学反应性的活化应变模型（ASM）对反应活性趋势进行了分析和解释。ASM已扩展用于处理溶液中的反应活性。这些发现有助于更合理地设计定制的取代反应。
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