直接连接的enyne二氧化的高度选择性的迪尔斯-阿尔德反应
Mingji Dai1, David Sarlah, Maolin Yu
1Department of Chemistry, Columbia University, Havemeyer Hall, New York, New York 10027, USA.
Journal of the American Chemical Society
|January 18, 2007
概括
迪尔斯-阿尔德反应与链接的enyne二烯基分子显示高选择性. 基部位的远程激活组决定了区域化学,使得天然产品基结构的合成成为可能.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
背景情况:
- 迪尔斯-阿尔德反应对于形成循环化合物至关重要.
- 在循环添加中,enynes 具有独特的反应性挑战.
研究的目的:
- 研究Diels-Alder反应的区域选择性,与相关的enyne二烯基分子有关.
- 了解激活组对循环加法结果的影响.
主要方法:
- 迪尔斯-阿尔德循环添加反应与替代的enyne二烯醇.
- 计算分析以解释观察到的反应性和选择性.
主要成果:
- 迪尔斯-阿尔德反应仅发生在enyne的乙烯基中心.
- 区域化学是由olefinic位点上的远程激活组主导的,取代了乙基上的组.
- 计算研究合理化了对乙环添加和远程组控制的偏好.
结论:
- 链接的enyne二烯醇在Diels-Alder反应中具有很高的选择性.
- 远程激活组对区域化学有很大的控制权.
- 这些发现开辟了新的合成途径,以获得烯酸盐类型的天然产品.
相关概念视频
Diels–Alder Reaction: Characteristics of Dienophiles
In a Diels–Alder reaction, the diene is usually an electron-rich system and acts as a nucleophile, whereas the dienophile is electron-deficient and functions as an electrophile. Much like the diene, the nature of the dienophile significantly impacts the outcome of the reaction.
Characteristics of Dienophiles
Generally, the best dienophiles are alkenes containing electron-withdrawing substituents such as carbonyl, nitrile, and nitro groups. The feasibility of a Diels–Alder reaction depends on...
Characteristics of Dienophiles
Generally, the best dienophiles are alkenes containing electron-withdrawing substituents such as carbonyl, nitrile, and nitro groups. The feasibility of a Diels–Alder reaction depends on...
Diels–Alder Reaction: Characteristics of Dienes
The Diels–Alder reaction brings together a diene and a dienophile to form a six-membered ring. Both components have unique characteristics that influence the rate of the reaction.
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
Diels–Alder vs Retro-Diels–Alder Reaction: Thermodynamic Factors
The Diels–Alder reaction is thermally reversible, meaning that the reaction reverts to the starting diene and dienophile under suitable temperatures. The forward reaction gives a cyclohexene derivative and is favored at low to medium temperatures. The reverse process, also called retro-Diels–Alder reaction, is a ring-opening process favored at high temperatures.


