预测高度异步的1,3-二极循环添加物的绝对速率常数的核友和电友性参数
Harish Jangra1, Quan Chen1, Elina Fuks1
1Department Chemie , Ludwig-Maximilians-Universität München , Butenandtstr. 5-13 , 81377 München , Germany.
Journal of the American Chemical Society
|November 17, 2018
概括
这项研究量化了aryldiazomethanes和benzhydrylium离子的反应动力学,建立了循环添加反应的预测模型. 这些发现揭示了反应机制以及电友性在化学运动中的作用.
科学领域:
- 有机化学
- 物理化学
- 化学动力学
背景情况:
- 阿里尔和离子是有机合成中的关键反应中间体.
- 了解它们的反应动力学对于预测反应结果和设计新的合成途径至关重要.
研究的目的:
- 调查阿里尔和离子之间的反应动力学.
- 开发基于电友性的1,3-双极循环添加反应的预测模型.
- 使用计算方法探索这些循环加法的机制细节.
主要方法:
- 用二甲测量反应动力学
- 紫外线光谱测定反应速度.
- 使用电友性参数 (E) 的相关性分析.
- 量子化学计算 (DFT) 来建模反应路径和能量.
主要成果:
- 二级速率常数与离子电友性线性相关.
- 一个预测方程 (lg k = sN(N + E)) 已建立用于确定二氧化化合物参数.
- 增量方法准确地预测了高度异步的循环添加率.
- 较弱的电友的偏差提供了协奏的能量 (ΔG).
- 计算研究证实了中间 Δ1 - 醇的形成和反应机制.
结论:
- 开发的动力模型准确地预测了各种循环添加的反应速率.
- 电友性是控制这些反应动学的关键因素.
- 计算方法,包括PCM溶解模型,适用于研究这些反应和预测激活能量.
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