Related Experiment Video
Updated: Feb 4, 2026
06:49
Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
Published on: April 22, 2016
12.4K
Ketyl radical reactivity via atom transfer catalysis.
Lu Wang1, Jeremy M Lear1, Sean M Rafferty1
1Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, USA.
Science (New York, N.Y.)
|October 13, 2018
Summary
Researchers developed a redox-neutral method for generating and reacting ketyl radicals from aldehydes. This strategy enables milder reaction conditions and access to vinyl iodide products via atom transfer radical addition.
Area of Science:
- Organic Chemistry
- Radical Chemistry
- Synthetic Methodology
Background:
- Ketyl radicals offer a polarity-reversed reactivity platform for carbonyl compounds.
- Current methods for ketyl radical generation require strong reductants, limiting synthetic utility to reductive pathways.
Purpose of the Study:
- To develop a net redox-neutral strategy for the generation and reaction of ketyl radicals.
- To enable milder reaction conditions and expand the reactivity of ketyl radicals.
Main Methods:
- In situ conversion of aldehydes to α-acetoxy iodides to lower reduction potentials.
- Visible light irradiation with a dimanganese decacarbonyl precatalyst.
- Atom Transfer Radical Addition (ATRA) mechanism.
Main Results:
- Achieved milder generation of ketyl radicals.
- Demonstrated an oxidative termination event.
- Synthesized a broad scope of vinyl iodide products with high Z-selectivity.
Conclusions:
- The developed strategy provides a versatile approach for ketyl radical chemistry.
- This method overcomes limitations of traditional reductive approaches.
- The atom transfer radical addition reaction offers a valuable route to functionalized vinyl iodides.
Related Concept Videos
02:50Catalysis
30.5K
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
30.5K
01:16Radical Reactivity: Nucleophilic Radicals
2.7K
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...
2.7K
01:02Radical Reactivity: Electrophilic Radicals
2.5K
Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a...
2.5K
01:11Radical Reactivity: Overview
2.8K
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...
2.8K
01:33Radical Reactivity: Intramolecular vs Intermolecular
2.2K
Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
2.2K
01:10Radical Reactivity: Steric Effects
2.5K
The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic...
Along with electronic...
2.5K