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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 Formation: Addition00:47

Radical Formation: Addition

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 unpaired...
Radical Formation: Overview01:03

Radical Formation: Overview

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 latter, also known...
Radical Formation: Elimination00:51

Radical Formation: Elimination

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 with respect to...
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...

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Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development
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Radical Sorting as a General Framework for Deaminative C(sp3)-C(sp2) Cross-Coupling.

Deepta Chattapadhyay1, En-Chih Liu1, Mark Jeffrey Diaz1

  • 1Department of Chemistry, Texas A&M University; College Station, Texas 77843, USA.

Chem
|May 25, 2026
PubMed
Summary
This summary is machine-generated.

This study introduces a new method for deaminative cross-coupling using primary amines as radical precursors. The dual-catalytic system enables selective C(sp3)-C(sp2) bond formation, expanding synthetic possibilities.

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10:12

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

Published on: April 4, 2014

Area of Science:

  • Organic Chemistry
  • Medicinal Chemistry
  • Catalysis

Background:

  • Radical-based cross-couplings are vital in medicinal chemistry.
  • Carboxylic acids are common radical precursors, but aliphatic primary amines are underutilized.
  • Developing new radical precursors is crucial for synthetic advancements.

Purpose of the Study:

  • To present a general method for deaminative cross-coupling of aliphatic primary amines.
  • To enable selective C(sp3)-C(sp2) bond formation using a dual-catalytic system.
  • To expand the scope of radical coupling reactions for amine functionalization.

Main Methods:

  • Utilized a dual-catalytic system involving photosensitization of unsymmetrical 1,2-dialkyldiazenes.
  • Generated geminate pairs of non-identical alkyl radicals.
  • Employed Nickel-mediated 'radical sorting' for selective C(sp3)-C(sp2) bond formation.
  • Integrated Sulfur(VI) Fluoride Exchange (SuFEx) click chemistry and the aza-Ramberg-Bäcklund reaction.

Main Results:

  • Achieved high yields in the cross-coupling of diverse primary amines.
  • Demonstrated selective engagement of desired radical species, minimizing side products.
  • Successfully functionalized peptide derivatives and pharmaceutical intermediates.
  • Showcased the versatility of the developed method for amine derivatization.

Conclusions:

  • The developed method provides a general and efficient route for deaminative cross-coupling of primary amines.
  • Nickel-mediated 'radical sorting' is key to the selectivity and high yields observed.
  • This approach broadens the utility of primary amines as building blocks in synthetic chemistry.
  • Mechanistic insights pave the way for novel radical-based cross-coupling strategies.