Jove
Visualize
Contact Us
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Concept Videos

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement01:21

[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement

2.7K
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.
2.7K
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction01:16

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

10.2K
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.
10.2K
Diels–Alder Reaction: Characteristics of Dienes01:29

Diels–Alder Reaction: Characteristics of Dienes

4.1K
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...
4.1K
Diels–Alder vs Retro-Diels–Alder Reaction: Thermodynamic Factors01:31

Diels–Alder vs Retro-Diels–Alder Reaction: Thermodynamic Factors

5.0K
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.
5.0K
Cycloaddition Reactions: Overview01:16

Cycloaddition Reactions: Overview

2.6K
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.
2.6K
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement01:24

[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement

2.1K
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.
2.1K

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

What is so special about benzene? A comparison of selected carbon and silicon isomers E<sub>6</sub>H<sub>6</sub> (E = C, Si).

Physical chemistry chemical physics : PCCP·2026
Same author

How Hexafluoroisopropanol Catalyzes the Michael Addition of Anilines to Maleimides: Mechanistic Insights from Density Functional Theory and Classical Force-Field Molecular Dynamics.

The Journal of organic chemistry·2026
Same author

Mechanism and Origin of Regioselectivity in Mn(I)-Catalyzed C-H Hydroarylation of 3-Substituted Aryloxazolines.

The Journal of organic chemistry·2026
Same author

Understanding the Electronic Structure and Diels-Alder Reactivity of Nitrilium-Type <i>N</i>-Hetarynes.

The Journal of organic chemistry·2026
Same author

Multicomponent Photochemical Assembly of C(sp<sup>2</sup>)-S Substituted Imidazoles via Exciplex Formation.

ACS organic & inorganic Au·2026
Same author

Heavier Alkyne-Ni<sup>0</sup> Complexes, [R<sub>2</sub>E<sub>2</sub>·Ni] (E = Sn, Pb), Exhibiting σ-Complex Character.

Angewandte Chemie (International ed. in English)·2026

Related Experiment Video

Updated: Jul 12, 2025

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
07:36

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy

Published on: November 9, 2019

8.0K

Mechanistic Insights into the DABCO-Catalyzed Cloke-Wilson Rearrangement: A DFT Perspective.

Sebastián Gallardo-Fuentes1, Lucas Lodeiro2, Ricardo Matute3

  • 1Instituto de Química, Facultad de Ciencias, Pontificia Universidad Católica de Valparaíso, Avenida Universidad 330, Curauma, Valparaíso 2373223, Chile.

The Journal of Organic Chemistry
|October 27, 2023
PubMed
Summary

Computational studies reveal the DABCO-catalyzed Cloke-Wilson rearrangement mechanism. The reaction proceeds stepwise, with regioselectivity influenced by cyclopropane substituents, explained by activation strain analysis.

More Related Videos

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid
07:06

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid

Published on: November 15, 2017

11.5K
Characterizing Lewis Pairs Using Titration Coupled with In Situ Infrared Spectroscopy
07:49

Characterizing Lewis Pairs Using Titration Coupled with In Situ Infrared Spectroscopy

Published on: February 20, 2020

9.2K

Related Experiment Videos

Last Updated: Jul 12, 2025

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
07:36

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy

Published on: November 9, 2019

8.0K
Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid
07:06

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid

Published on: November 15, 2017

11.5K
Characterizing Lewis Pairs Using Titration Coupled with In Situ Infrared Spectroscopy
07:49

Characterizing Lewis Pairs Using Titration Coupled with In Situ Infrared Spectroscopy

Published on: February 20, 2020

9.2K

Area of Science:

  • Organic Chemistry
  • Computational Chemistry

Background:

  • The Cloke-Wilson rearrangement is a valuable synthetic transformation.
  • Understanding its mechanism and selectivity is crucial for its application.

Purpose of the Study:

  • To elucidate the detailed mechanism of the DABCO-catalyzed Cloke-Wilson rearrangement.
  • To investigate the factors governing regioselectivity in the reaction.
  • To explore alternative mechanisms for vinylcyclopropane analogs.

Main Methods:

  • Density Functional Theory (DFT) calculations.
  • Activation Strain Model-Energy Decomposition Analysis (ASM-EDA).

Main Results:

  • The reaction proceeds stepwise via cyclopropane ring opening by DABCO, followed by zwitterionic intermediate ring closure.
  • Regioselectivity is substituent-dependent, favoring the more hindered tertiary position.
  • A novel SN2' ring-opening and 5-exo-trig cyclization mechanism was identified for vinylcyclopropanes.

Conclusions:

  • DFT calculations provide a detailed mechanistic and selectivity profile for the DABCO-catalyzed Cloke-Wilson rearrangement.
  • The study quantifies the physical factors influencing regioselectivity.
  • A new reaction pathway for vinylcyclopropane derivatives was discovered.