同步的芳香度作为芳香Cope重排的力驱动力
David J Babinski1, Xiaoguang Bao, Marie El Arba
1Department of Chemistry, The University of Texas at San Antonio, San Antonio, Texas 78249, USA.
Journal of the American Chemical Society
|September 12, 2012
概括
这项研究提供了芳香Cope重组的证据,包括首次隔离关键中间体. 皮拉环形成在温和条件下驱动这些反应.
科学领域:
- 有机化学 有机化学
- 反应机制 反应机制
- 计算化学计算化学
背景情况:
- 应对重组是基本的有机反应.
- 芳香Cope重组的理解较少.
- 反应中间体的表征对于机理学研究至关重要.
研究的目的:
- 为芳香Cope重组提供实验和理论证据.
- 为了分离和描述在 [3,3] 西格马特罗普重新排列后形成的中间体.
- 为了阐明芳香Cope重组背后的驱动力.
主要方法:
- 实验性有机合成和表征.
- 密度函数理论 (DFT) 的计算 (B3LYP/6-31G(d)).
- 对反应能量障碍和热力学贡献的分析.
主要成果:
- 成功执行芳香Cope重组,并隔离了一个关键的中间体.
- 反应能量障碍 (22-23 kcal/mol) 与实验轻度条件对齐的计算预测.
- 识别pyrazole环形成作为一个显著的体驱动力.
结论:
- 这项研究证实了芳香Cope重组具有强大的实验和理论支持.
- 皮拉环形成被确定为一个关键因素,提供动力和热力学动力.
- 这项工作有助于我们更好地理解芳香系统中的西格马特罗普再排列.
相关概念视频
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
Electrophilic Aromatic Substitution: Overview
In an electrophilic aromatic substitution reaction, an electrophile substitutes for a hydrogen of an aromatic compound.
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.
Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)
Nucleophilic substitution in aromatic compounds is feasible in substrates bearing strong electron-withdrawing substituents positioned ortho or para to the leaving group. The reaction proceeds via two steps: the addition of the nucleophile and the elimination of the leaving group.
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between the...
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between the...
π Electron Effects on Chemical Shift: Aromatic and Antiaromatic Compounds
In aromatic compounds, such as benzene, the circulation of (4n + 2) π-electrons sets up a diamagnetic or diatropic ring current around the perimeter of the molecule. This current induces a magnetic field that opposes the external field inside the ring and reinforces it on the outside. The protons in benzene are deshielded and exhibit high chemical shifts in the range 6.5–8.5 ppm. The shielding effect at the center of the ring is evident in complex aromatic molecules, such as annulenes. In...
Criteria for Aromaticity and the Hückel 4n + 2 Rule
Like benzene, cyclobutadiene and cyclooctatetraene are cyclic compounds with alternate single and double bonds. However, their chemical behavior differs from benzene, as they are unstable and not aromatic. So, what are the structural characteristics of unsaturated compounds categorized as aromatic?
For the first time, Eric Hückel, a German chemical physicist, derived a set of structural features for a compound to be classified as aromatic. This is now known as Hückel’s rule or the 4n + 2 rule.
For the first time, Eric Hückel, a German chemical physicist, derived a set of structural features for a compound to be classified as aromatic. This is now known as Hückel’s rule or the 4n + 2 rule.


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