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相关概念视频

[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction01:16

[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction

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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.
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Cycloaddition Reactions: Overview01:16

Cycloaddition Reactions: Overview

3.4K
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
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Diels–Alder Reaction Forming Cyclic Products: Stereochemistry01:28

Diels–Alder Reaction Forming Cyclic Products: Stereochemistry

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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.
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Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry01:29

Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry

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Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
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Diels–Alder Reaction: Characteristics of Dienes01:29

Diels–Alder Reaction: Characteristics of Dienes

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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,...
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Diels–Alder Reaction: Characteristics of Dienophiles01:24

Diels–Alder Reaction: Characteristics of Dienophiles

7.2K
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...
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Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
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Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes

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在Diels-Alder循环添加中,以机器学习为指导的结构反应关系的研究.

Amir Mahdian1, Kaveh Farshadfar1, Kari Laasonen1

  • 1Department of Chemistry and Material Science, School of Chemical Engineering, Aalto University, Espoo 02150, Finland.

The Journal of organic chemistry
|January 7, 2026
PubMed
概括

这项研究揭示了固体效应,特别是对内部二烯碳的替代剂体积,显著影响了Diels-Alder反应障碍. 电子因素,如边境分子轨道能量差距,也在预测反应性方面发挥着作用.

科学领域:

  • 有机化学 有机化学
  • 计算化学计算化学
  • 化学反应性 化学反应性

背景情况:

  • 迪尔斯-阿尔德循环添加是有机合成中的一个基本反应.
  • 了解影响其反应性和激活障碍的因素对于合成设计至关重要.
  • 之前的研究已经探讨了电子和固态效应,但结合计算方法提供了新的见解.

研究的目的:

  • 通过计算来研究固体和电子效应对迪尔斯-阿尔德反应激活障碍物的相互作用.
  • 开发使用分子描述器对迪尔斯-阿尔德反应性的预测模型.
  • 确定控制反应结果的关键分子特征.

主要方法:

  • 密度函数理论 (DFT) 计算以获得激活能量.
  • 机器学习模型在1000个未催化碳化合物迪尔斯-阿尔德反应的数据集上进行训练.
  • 通过SHAP (夏普利添加式解释) 分析来解释模型预测,并识别重要的分子描述符.

主要成果:

  • 发现效应,特别是内部二烯碳中的替代体量,是影响激活障碍的主要因素.
  • 终端位置的替代剂对反应能力的影响不那么大.
  • 边界分子轨道 (LUMOdiene-HOMO dienophile和LUMO dienophile-HOMO diene) 之间的最小能量差距成为一个关键的预测描述符,与激活能量相关.

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  • 绝缘相互作用可能会导致单纯由电子因素预测的趋势的偏差.
  • 结论:

    • 内部二烯碳的固体阻碍是迪尔斯-阿尔德反应中活性障碍升高的主要驱动因素.
    • 结合DFT和机器学习的预测模型可以有效地合理化Diels-Alder反应性.
    • 获得的见解可以通过对硬质和电子性质的战略操纵来指导更有效的循环加法反应的合理设计.