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Related Concept Videos

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

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

12.1K
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

4.7K
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

5.0K
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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A Machine Learning-Guided Study of Structure-Reactivity Relationships in Diels-Alder Cycloadditions.

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
Summary
This summary is machine-generated.

This study reveals steric effects, especially substituent volume on internal diene carbons, significantly impact Diels-Alder reaction barriers. Electronic factors, like frontier molecular orbital energy gaps, also play a role in predicting reactivity.

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Area of Science:

  • Organic Chemistry
  • Computational Chemistry
  • Chemical Reactivity

Background:

  • The Diels-Alder cycloaddition is a fundamental reaction in organic synthesis.
  • Understanding factors influencing its reactivity and activation barriers is crucial for synthetic design.
  • Previous studies have explored electronic and steric effects, but a combined computational approach offers new insights.

Purpose of the Study:

  • To computationally investigate the interplay of steric and electronic effects on Diels-Alder reaction activation barriers.
  • To develop predictive models for Diels-Alder reactivity using molecular descriptors.
  • To identify key molecular features governing reaction outcomes.

Main Methods:

  • Density Functional Theory (DFT) calculations to obtain activation energies.
  • Machine learning models trained on a dataset of 1000 uncatalyzed hydrocarbon Diels-Alder reactions.
  • SHAP (SHapley Additive exPlanations) analysis to interpret model predictions and identify important molecular descriptors.

Main Results:

  • Steric effects, particularly substituent volume at internal diene carbons, were found to be the dominant factor influencing activation barriers.
  • Substituents at terminal positions showed a less significant impact on reactivity.
  • The minimum energy gap between frontier molecular orbitals (LUMOdiene-HOMO dienophile and LUMO dienophile-HOMO diene) emerged as a key predictive descriptor, correlating well with activation energy.
  • Steric interactions can cause deviations from the trend predicted by electronic factors alone.

Conclusions:

  • Steric hindrance at internal diene carbons is a primary driver of elevated activation barriers in Diels-Alder reactions.
  • Predictive models combining DFT and machine learning can effectively rationalize Diels-Alder reactivity.
  • Insights gained can guide the rational design of more efficient cycloaddition reactions through strategic manipulation of steric and electronic properties.