迈克尔受体的电友性的定量化和理论分析
Dominik S Allgäuer1, Harish Jangra1, Haruyasu Asahara1
1Department Chemie, Ludwig-Maximilians-Universität München , Butenandtstrasse 5-13, 81377 München, Germany.
Journal of the American Chemical Society
|September 19, 2017
概括
这项研究使用动力数据和核友参数量化了迈克尔受体的电友反应. 计算的电友性参数 (E) 预测反应速率,甲基离子亲和力显示出强烈的反应性估计相关性.
科学领域:
- 有机化学
- 物理化学
- 计算化学
背景情况:
- 迈克尔受体在有机合成中至关重要,但它们的电友反应性有很大差异.
- 量化这些反应性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:
- 为常见的迈克尔受体开发电友反应性的定量测量.
- 建立基于经验电友性参数的反应速率预测模型.
主要方法:
- 测量了与化,硫化和甲基离子替代乙烯和烯的反应动力.
- 使用相关方程 (log k = sN(E + N)) 来计算新的经验电友性参数 (E).
- 使用密度函数理论 (DFT) 计算来研究反应机制和反应源.
主要成果:
- 为迈克尔受体确定了15个新的经验电友性参数 (E).
- 在不同的核爱者-迈克尔受体反应中展示了一个共同的速率决定步骤.
- 在实验电友反应和计算的甲基离子亲和度之间发现了强烈的相关性,特别是在SMD溶解中.
结论:
- 开发的电友性参数 (E) 可以准确地预测迈克尔受体的反应速率.
- 甲基离子亲和度作为快速估计迈克尔受体电友反应性的可靠方法.
- 这些发现为理解和预测迈克尔加法反应的反应性提供了强有力的框架.
相关概念视频
Conjugate Addition of Enolates: Michael Addition
3.7K
The attack of a nucleophile at the β carbon of an α,β-unsaturated carbonyl compound is called conjugate addition. Conjugate addition reactions of active methylene compounds, such as β-diketones, β-keto esters, β-keto nitriles, and α-nitro ketones, are called Michael addition reactions.
3.7K
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
17.7K
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
17.7K
Electrophiles
12.9K
This lesson explains the definition, classification, and characteristic features of an electrophile that are key features of nucleophilic substitution reactions. An analysis of their charge and orbital picture helps understand their reactivity for seeking electrons. Electrophiles can be classified into positive and neutral species. Other classes include free radicals and polar functional groups.
While a positive electrophile, like a proton, reacts due to its vacant, low-energy 1s orbital, the...
While a positive electrophile, like a proton, reacts due to its vacant, low-energy 1s orbital, the...
12.9K
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
7.7K
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
7.7K
Radical Reactivity: Electrophilic Radicals
2.5K
Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a...
2.5K
Electrophilic Aromatic Substitution: Overview
14.8K
In an electrophilic aromatic substitution reaction, an electrophile substitutes for a hydrogen of an aromatic compound.
14.8K


