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Related Concept Videos

Radical Formation: Homolysis00:54

Radical Formation: Homolysis

A bond is formed between two atoms by sharing two electrons. When this bond is broken by supplying sufficient energy, either two electrons can be taken up by one atom forming ions by the cleavage called heterolysis, or the two electrons are shared by two atoms, with one each creating radicals by the cleavage called homolysis.
Regioselectivity of Electrophilic Additions-Peroxide Effect02:35

Regioselectivity of Electrophilic Additions-Peroxide Effect

In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids02:04

Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
Radical Formation: Elimination00:51

Radical Formation: Elimination

Another method of radical formation is the elimination process. It is the opposite of the addition route and is driven by the instability of the radical. For example, as depicted in Figure 1, dibenzoyl peroxide yields a pair of unstable radicals upon homolysis. Given its instability, this radical spontaneously undergoes elimination via a C–C bond cleavage to form a relatively more stable phenyl radical. The mechanism involves cleavage of the bond between the α and β positions with respect to...
Radical Autoxidation01:20

Radical Autoxidation

The oxidation of an organic compound in the presence of air or oxygen is called autoxidation. For example, cumene reacts with oxygen to form hydroperoxide. Autoxidation involves initiation, propagation, and termination steps. Many organic compounds are susceptible to autoxidation—especially ethers in the presence of oxygen, which form hydroperoxides. Even though this reaction is slow, old ether bottles contain small amounts of peroxide, which leads to laboratory explosions during ether...
Radical Anti-Markovnikov Addition to Alkenes: Mechanism01:17

Radical Anti-Markovnikov Addition to Alkenes: Mechanism

The reaction of hydrogen bromide with alkenes in the presence of hydroperoxides or peroxides proceeds via anti-Markovnikov addition. The radical chain reaction comprises initiation, propagation, and termination steps.
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy radical...

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Updated: May 12, 2026

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides (CHIPS)
06:34

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides (CHIPS)

Published on: June 20, 2014

Molecule-induced peroxide homolysis.

Natascia Turrà1, Ulrich Neuenschwander, Ive Hermans

  • 1Department of Chemistry and Applied Biosciences, ETH Zurich, Wolfgang-Pauli-Strasse 10, HCI E131, Switzerland.

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
|April 6, 2013
PubMed
Summary
This summary is machine-generated.

Free radicals form from peroxide bond cleavage, driving hydrocarbon oxidation. This study reveals a molecule-induced homolytic dissociation mechanism involving alkyl peroxides and unsaturated hydrocarbons.

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Area of Science:

  • Organic Chemistry
  • Physical Chemistry
  • Reaction Mechanisms

Background:

  • Homolytic cleavage of peroxide bonds generates free radicals, crucial in hydrocarbon oxidation.
  • Aerobic oxidation of hydrocarbons can be industrially beneficial (autoxidation) or detrimental (food spoilage).

Purpose of the Study:

  • To provide evidence for a molecule-induced homolytic dissociation mechanism.
  • To investigate the interaction between alkyl peroxides and compounds with weakly bonded H atoms.

Main Methods:

  • Experimental investigations of reaction pathways.
  • Computational modeling to support mechanistic understanding.

Main Results:

  • Demonstrated a molecule-induced homolytic dissociation mechanism.
  • Identified (di)unsaturated hydrocarbons as key facilitators due to weakly bonded H atoms.

Conclusions:

  • The study elucidates a novel mechanism for initiating free radical formation.
  • Understanding this mechanism is vital for controlling desired and undesired oxidation processes.