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Related Concept Videos

Radical Reactivity: Overview01:11

Radical Reactivity: Overview

2.1K
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...
2.1K
Radical Formation: Addition00:47

Radical Formation: Addition

1.8K
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...
1.8K
Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

1.8K
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...
1.8K
Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

2.0K
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...
2.0K
Radical Formation: Overview01:03

Radical Formation: Overview

2.1K
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...
2.1K
Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

2.2K
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...
2.2K

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

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Radical C(sp3)-H functionalization and cross-coupling reactions.

Dung L Golden1,2, Sung-Eun Suh1,2,3, Shannon S Stahl1

  • 1Department of Chemistry, University of Wisconsin-Madison, WI, USA.

Nature Reviews. Chemistry
|August 15, 2022
PubMed
Summary
This summary is machine-generated.

Radical C─H functionalization reactions are advancing organic synthesis. Emerging radical-relay methods enable versatile intermolecular C(sp3)─H functionalization and cross-coupling for complex molecules.

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Area of Science:

  • Organic Chemistry
  • Synthetic Chemistry

Background:

  • C─H functionalization is crucial for creating complex organic molecules like pharmaceuticals and agrochemicals.
  • Radical C─H functionalization, using hydrogen-atom transfer (HAT), offers strategic ways to modify C(sp3)─H bonds.

Purpose of the Study:

  • To review recent advances in radical-chain and radical-rebound C─H functionalization.
  • To survey emerging radical-relay methods for intermolecular C(sp3)─H functionalization and cross-coupling.

Main Methods:

  • Review of literature on radical-chain and radical-rebound reactions.
  • Analysis of emerging radical-relay mechanisms involving diffusible radicals.

Main Results:

  • Radical-chain and radical-rebound methods have shown significant synthetic utility.
  • Radical-relay strategies expand the scope of intermolecular C(sp3)─H functionalization.

Conclusions:

  • Radical-relay methods represent a significant expansion in C─H functionalization capabilities.
  • These methods enhance the versatility of cross-coupling reactions with diverse partners.