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Related Concept Videos

Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

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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...
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Source: Vy M. Dong and Daniel Kim, Department of Chemistry, University of California, Irvine, CA
Nucleophilic substitution reactions are among the most fundamental topics covered in organic chemistry. A nucleophilic substitution reaction is one where a nucleophile (electron-rich Lewis base) replaces a leaving group from a carbon atom.
SN1 (S = Substitution, N = Nucleophilic, 1 = first-order kinetics)
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The word “nucleophile” has a Greek root and translates to nucleus-loving. Nucleophiles are either negatively charged or neutral species with a pair of electrons in a high-energy occupied molecular orbital (HOMO). As these species tend to donate electron pairs, nucleophiles are considered Lewis bases as well. Negatively charged species, like OH−, Cl−, or HS−, with one or several pairs of electrons, are typically nucleophiles. Similarly, neutral species such as...
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Historical perspective
In 1896, the German chemist Paul Walden discovered that he could interconvert pure enantiomeric (+) and (-) malic acids through a series of reactions. This conversion suggested the involvement of optical inversion during the substitution reaction. Further, in 1930, Sir Christopher Ingold described for the first time two different forms of nucleophilic substitution reactions, which are known as SN1 (nucleophilic substitution unimolecular) and SN2 (nucleophilic substitution...
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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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Related Experiment Video

Updated: Jan 20, 2026

Radical Reactivity: Nucleophilic Radicals
01:16

Radical Reactivity: Nucleophilic Radicals

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Radical-Stimulated Nucleophile Release.

John C Walton1

  • 1EaStCHEM School of Chemistry , University of St. Andrews , St. Andrews , Fife KY16 9ST , United Kingdom.

The Journal of Organic Chemistry
|September 6, 2019
PubMed
Summary
This summary is machine-generated.

Radicals adjacent to positive charges can enhance inverse heterolytic dissociation, facilitating nucleophile release. This effect is stronger with carbon-centered radicals and has implications for DNA/RNA strand scission.

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Area of Science:

  • Organic Chemistry
  • Computational Chemistry
  • Biochemistry

Background:

  • Radical centers are known to enhance deprotonation.
  • Inverse heterolytic dissociation releases nucleophiles, unlike typical heterolytic dissociation.

Purpose of the Study:

  • To investigate if radicals can stimulate inverse heterolytic dissociations.
  • To assess the impact of radical proximity and type on dissociation enhancement.

Main Methods:

  • Density Functional Theory (DFT) calculations were used.
  • Free energies of heterolytic dissociations were assessed.
  • Various radical-containing precursors were computationally examined.

Main Results:

  • Radicals adjacent to incipient positive charges generally enhanced heterolytic dissociation.
  • Carbon-centered radicals showed greater enhancement than oxygen-centered radicals.
  • Specific precursors (fluorenylmethyl, cyclohepta-2,4,6-trienylmethyl) enabled exergonic nucleophile release.
  • Enhanced heterolytic phosphate release from nucleotide C4' radicals was observed, supporting DNA/RNA strand breaking mechanisms.
  • Resonance stabilization of radical-cations was identified as the key promoting factor.

Conclusions:

  • Suitably sited radicals can significantly enhance inverse heterolytic dissociation.
  • This mechanism is relevant to radical-induced DNA and RNA strand breaking.
  • Understanding these effects aids in designing molecules with controlled dissociation properties.