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Radical Formation: Homolysis00:54

Radical Formation: Homolysis

4.6K
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.
4.6K
Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

2.8K
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
2.8K
Alkynes to Carboxylic Acids: Oxidative Cleavage02:01

Alkynes to Carboxylic Acids: Oxidative Cleavage

7.2K
Alkynes undergo oxidative cleavage in the presence of oxidizing reagents like potassium permanganate and ozone. The triple bond — one σ bond and two π bonds — is completely cleaved, and the alkyne is oxidized to carboxylic acids. When warm and basic aqueous potassium permanganate is used as an oxidizing agent, alkynes are first converted to carboxylate salts via an unstable α-diketone intermediate. Further, a mild acid treatment protonates the carboxylate anions...
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Radical Formation: Overview01:03

Radical Formation: Overview

2.7K
A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
2.7K
Radical Reactivity: Overview01:11

Radical Reactivity: Overview

3.0K
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
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Radical Formation: Addition00:47

Radical Formation: Addition

2.4K
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
2.4K

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Related Experiment Video

Updated: Apr 15, 2026

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
06:49

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

Published on: April 22, 2016

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Visible-Light-Induced C-S Bond Cleavage Enables Alkyl Radical Generation from Redox-Inert Substrates.

Ryo Yanagida1, Valero Gimeno Alfonso2, Justin Ching3

  • 1Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan.

Journal of the American Chemical Society
|April 14, 2026
PubMed
Summary

This study introduces a novel visible-light method for generating alkyl radicals from unreactive compounds. It utilizes sulfur intermediates for efficient C-S bond cleavage, enabling new synthetic pathways without external photocatalysts.

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Light-driven Enzymatic Decarboxylation
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Light-driven Enzymatic Decarboxylation
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Area of Science:

  • Organic Chemistry
  • Photochemistry
  • Radical Chemistry

Background:

  • Alkyl radical generation is crucial for carbon-carbon bond formation.
  • Activating redox-inert substrates like alkyl chlorides and epoxides remains challenging.
  • Existing methods often require photocatalysts or harsh conditions.

Purpose of the Study:

  • To develop a visible-light-driven platform for alkyl radical generation.
  • To activate typically unreactive substrates without external photocatalysts.
  • To demonstrate the utility of generated radicals in C-C bond-forming reactions.

Main Methods:

  • Employing thioethers derived from alkenes as precursors.
  • Utilizing visible-light irradiation to induce photoinduced excitation and C-S bond cleavage.
  • Investigating mechanistic pathways involving sulfur-based anionic intermediates.

Main Results:

  • Efficient homolytic C-S bond cleavage in thioethers under visible light.
  • Successful generation of alkyl radicals from unactivated alkyl chlorides and epoxides.
  • Demonstration of metal-free alkenylation reactions using the generated radicals.

Conclusions:

  • Sulfur-mediated photoactivation offers a versatile route to alkyl radical chemistry.
  • This method enables radical generation from readily available, redox-inert substrates.
  • The platform avoids the need for external photocatalysts or stoichiometric additives.