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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

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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 Chain-Growth Polymerization: Overview01:10

Radical Chain-Growth Polymerization: Overview

2.8K
Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
2.8K
Radical Formation: Elimination00:51

Radical Formation: Elimination

1.9K
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...
1.9K
Radical Formation: Overview01:03

Radical Formation: Overview

2.3K
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...
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Free-Radical Chain Reaction and Polymerization of Alkenes02:35

Free-Radical Chain Reaction and Polymerization of Alkenes

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The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
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Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
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Evolution towards green radical generation in total synthesis.

Matthew S Galliher1, Bec J Roldan1, Corey R J Stephenson1

  • 1Department of Chemistry, University of Michigan, 930 N. University Ave, Ann Arbor, MI 48109, USA. crjsteph@umich.edu.

Chemical Society Reviews
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Summary

Radical chemistry in total synthesis has advanced from metal hydrides to greener methods like photoredox catalysis. This review covers classical and modern radical generation techniques and their use in synthesizing complex molecules.

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Area of Science:

  • Organic Chemistry
  • Synthetic Chemistry

Background:

  • Radical intermediates have been crucial in organic synthesis since the mid-20th century.
  • Traditional radical generation often relied on stoichiometric metal hydride reagents.

Purpose of the Study:

  • To review the evolution of radical generation methods in total synthesis.
  • To highlight contemporary "greener" approaches and their applications.

Main Methods:

  • Discussion of classical radical generation techniques.
  • Overview of modern catalytic metal-mediated systems.
  • Exploration of electrochemical and photoredox-mediated radical generation.

Main Results:

  • Shift from stoichiometric to catalytic and sustainable radical generation methods.
  • Demonstration of diverse applications of these methods in total synthesis.
  • Integration of classical and contemporary radical strategies.

Conclusions:

  • Modern radical generation offers efficient and environmentally benign pathways for complex molecule synthesis.
  • The reviewed methods provide valuable tools for synthetic chemists.
  • Continued innovation in radical chemistry is vital for advancing total synthesis.