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Related Concept Videos

Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

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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...
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Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

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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...
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Phosphorylation01:02

Phosphorylation

50.3K
The addition or removal of phosphate groups from proteins is the most common chemical modification that regulates cellular processes. These modifications can affect the structure, activity, stability, and localization of proteins within cells as well as their interactions with other proteins.
During phosphorylation, protein kinases transfer the terminal phosphate group of ATP to specific amino acid side chains of substrate proteins. Serine, threonine, and tyrosine are the most commonly...
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Radical Reactivity: Overview01:11

Radical Reactivity: Overview

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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

1.7K
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...
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Radical Formation: Elimination00:51

Radical Formation: Elimination

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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...
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Related Experiment Video

Updated: Jul 6, 2025

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Photoinduced Decarboxylative Radical Phosphinylation.

Yulu Cheng1, Jingsen Zhen2, Linxiang Chai1

  • 1Department of Chemistry, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026, China.

Angewandte Chemie (International Ed. in English)
|January 5, 2024
PubMed
Summary

This study introduces a new method for C(sp3)-phosphinylation using visible light and a catalyst. The reaction efficiently synthesizes bioactive phosphinic acids from common precursors.

Keywords:
DecarboxylationPhosphinylationPhotoredox CatalysisRadicals

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Area of Science:

  • Organic Chemistry
  • Catalysis
  • Synthetic Methodology

Background:

  • C(sp3)-phosphinylation is a crucial transformation for synthesizing organophosphorus compounds.
  • Existing methods often require harsh conditions or lack substrate scope.

Purpose of the Study:

  • To develop an unprecedented, mild, and efficient protocol for C(sp3)-phosphinylation.
  • To enable the late-stage functionalization of complex molecules and synthesis of bioactive phosphinic acids.

Main Methods:

  • Visible light-induced reaction catalyzed by 4CzIPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene).
  • Utilized redox-active esters of aliphatic carboxylic acids and phosphonites.
  • Operated at room temperature with low catalyst loading (1 mol%).

Main Results:

  • Achieved satisfactory yields of decarboxylative phosphinylation products.
  • Demonstrated broad substrate scope and wide functional-group compatibility.
  • Successfully synthesized bioactive phosphinic acids, including phosphinothricin and a kynureninase inhibitor.

Conclusions:

  • The developed protocol offers a novel and versatile route to C(sp3)-phosphinylated compounds.
  • A radical-polar crossover mechanism is proposed, involving phosphoranyl radicals and nucleophilic demethylation/deethylation.
  • This method facilitates the synthesis of complex organophosphorus molecules and drug candidates.