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Related Concept Videos

Radical Reactivity: Overview01:11

Radical Reactivity: Overview

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 molecule. These three...
Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

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 factors, steric factors also account...
Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

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 instance, consider...
Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

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 low‐energy SOMO, which interacts...
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction01:22

Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction

The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

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 carbon–halogen...

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Updated: Jun 6, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
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Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Published on: June 21, 2017

Stereoretentive radical-based alkyl-alkyl cross-coupling.

Yu Wang1, Jiawei Sun1, Yin Li1

  • 1Department of Chemistry, Scripps Research, La Jolla, CA, USA.

Science (New York, N.Y.)
|June 4, 2026
PubMed
Summary
This summary is machine-generated.

This study introduces a novel method for stereoretentive radical-radical cross-coupling, creating stereogenic C(sp3)-C(sp3) bonds with high enantiospecificity. The nickel-catalyzed reaction efficiently couples alkyl radicals without chiral ligands, offering a scalable solution for complex molecule synthesis.

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Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
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Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions

Published on: March 20, 2014

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Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
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Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

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Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
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Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

Published on: April 4, 2014

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
11:44

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions

Published on: March 20, 2014

Area of Science:

  • Organic Chemistry
  • Catalysis
  • Synthetic Methodology

Background:

  • Constructing stereogenic C(sp3)-C(sp3) bonds via cross-coupling is challenging due to competing side reactions and poor stereocontrol in radical pathways.
  • Existing methods often require chiral ligands or directing groups, limiting their scope and efficiency.

Purpose of the Study:

  • To develop a scalable and stereoretentive method for radical-radical cross-coupling of distinct alkyl radicals.
  • To achieve high enantiospecificity in C(sp3)-C(sp3) bond formation without relying on chiral auxiliaries or exogenous redox agents.

Main Methods:

  • Utilized enantioenriched sulfonylhydrazides and achiral alkyl halides as radical precursors.
  • Employed a nickel-catalyzed, redox-neutral manifold for controlled radical generation and cross-coupling.
  • Investigated mechanistic pathways involving diazene-mediated radical generation and halogen atom transfer.

Main Results:

  • Achieved stereoretentive radical-radical cross-coupling with enantiospecificities ranging from 80% to 96%.
  • Obtained synthetically useful yields up to 90% for diverse piperidine and pyrrolidine scaffolds.
  • Demonstrated tolerance for various functional groups including ethers, amines, aryl halides, and olefins.

Conclusions:

  • The substrate-controlled approach enables efficient and stereospecific formation of C(sp3)-C(sp3) bonds.
  • Caged radical rebound at nickel is proposed to preserve chirality during the cross-coupling process.
  • The developed method offers a valuable tool for synthesizing complex chiral molecules with high fidelity.