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Related Concept Videos

Cycloaddition Reactions: Overview01:16

Cycloaddition Reactions: Overview

3.6K
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.
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Cycloaddition Reactions: MO Requirements for Thermal Activation01:16

Cycloaddition Reactions: MO Requirements for Thermal Activation

4.7K
Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
4.7K
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement01:21

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

3.5K
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.
3.5K
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction01:22

Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction

2.4K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
2.4K
Cycloaddition Reactions: MO Requirements for Photochemical Activation01:12

Cycloaddition Reactions: MO Requirements for Photochemical Activation

2.8K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
2.8K
Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

3.1K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
3.1K

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Updated: Feb 18, 2026

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
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Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene

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Cobalt- and Silver-Promoted Methylenecyclopropane Rearrangements.

Xavier Creary1

  • 1Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.

The Journal of Organic Chemistry
|November 29, 2017
PubMed
Summary
This summary is machine-generated.

Cobalt complexes and silver cations accelerate methylenecyclopropane rearrangement by stabilizing reactive intermediates. Computational studies reveal spin delocalization mechanisms are key to this rate enhancement.

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Area of Science:

  • Organometallic Chemistry
  • Reaction Mechanism Studies
  • Computational Chemistry

Background:

  • The methylenecyclopropane rearrangement is a fundamental organic transformation.
  • Understanding factors that influence its reaction rate is crucial for synthetic applications.
  • Previous studies have explored various catalytic systems for this rearrangement.

Purpose of the Study:

  • To investigate the rate-enhancing effects of alkyne-cobalt complexes on methylenecyclopropane rearrangement.
  • To explore the role of silver cations in promoting the same reaction.
  • To elucidate the mechanistic pathways involved using computational studies.

Main Methods:

  • Experimental kinetic studies of methylenecyclopropane rearrangement in the presence of alkyne-Co2(CO)6 complexes.
  • Kinetic studies with silver cations, including a series of aryl-substituted methylenecyclopropanes.
  • Density Functional Theory (DFT) calculations to model transition states and intermediates.

Main Results:

  • Alkyne-Co2(CO)6 complexes significantly enhance the rearrangement rate, attributed to transition state stabilization.
  • Computational analysis indicates spin delocalization onto cobalt atoms stabilizes the biradical intermediate.
  • Silver cations also accelerate the reaction, with rate enhancements correlating to substituent electronic effects (σ+).

Conclusions:

  • Both alkyne-cobalt complexes and silver cations effectively catalyze methylenecyclopropane rearrangement.
  • Stabilization of reaction intermediates, particularly biradicals, via spin delocalization is a key mechanistic feature.
  • The precise mechanism of silver catalysis (biradical vs. carbocation intermediate) requires further investigation.