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Related Concept Videos

Radical Halogenation: Stereochemistry01:33

Radical Halogenation: Stereochemistry

3.7K
Stereochemistry is the study of the different spatial arrangements of atoms in a given molecule. The stereochemistry of radical halogenations can be understood from three different situations:
Halogenation to form a new chiral center:
3.7K
Radical Halogenation: Thermodynamics01:34

Radical Halogenation: Thermodynamics

3.7K
The thermodynamic favorability of a reaction is determined by the change in Gibbs free energy (ΔG). ΔG has two components- enthalpy (ΔH) and entropy (ΔS). The entropy component is negligible for alkane halogenation because the number of reactants and product molecules are equal. In this case, the ΔG is governed only by the enthalpy component. The most crucial factor that determines ΔH is the strength of the bonds. ΔH can be determined by comparing the energy...
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Radical Reactivity: Nucleophilic Radicals01:16

Radical Reactivity: Nucleophilic Radicals

2.1K
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...
2.1K
Radical Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

1.9K
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...
1.9K
Radical Substitution: Allylic Chlorination01:31

Radical Substitution: Allylic Chlorination

2.2K
Typically, when alkenes react with halogens at low temperatures, an addition reaction occurs. However, upon increasing the temperature or under reaction conditions that form radicals, providing a low but steady concentration of halogen radicals, allylic substitution reaction is favored. This is because allylic hydrogens are very reactive as the formed intermediate is resonance stabilized. For example, when propene is treated with chlorine in the gas phase at 400 °C, it undergoes allylic...
2.2K
Radical Reactivity: Concentration Effects01:20

Radical Reactivity: Concentration Effects

1.5K
In a radical reaction, the concentration of starting materials governs the selectivity of a radical. For example, the reaction between an alkyl halide and an alkene, in the presence of tin hydride and AIBN, begins with the generation of a tin radical. The generated radical then abstracts halogen from the alkyl halide, producing an alkyl radical. This alkyl radical can either react with tin hydride, yielding an alkane, or add to an alkene, generating a nitrile-stabilized radical, eventually...
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Related Experiment Video

Updated: Jun 11, 2025

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
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Dynamic metal coordination controls chemoselectivity in radical halogenases.

Elijah N Kissman, Ioannis Kipouros, Jeffrey W Slater

    Biorxiv : the Preprint Server for Biology
    |September 30, 2024
    PubMed
    Summary

    Non-heme iron enzymes activate C-H bonds for crucial biological processes. This study reveals a minimal two-residue motif driving catalytic plasticity in iron-dependent radical halogenases.

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    Area of Science:

    • Biochemistry and enzymology
    • Chemical biology
    • Organic synthesis

    Background:

    • Non-heme iron enzymes catalyze the activation of inert C(sp³)-H bonds, essential for metabolism, epigenetics, and signaling.
    • Fe(II)/α-ketoglutarate-dependent radical halogenases are biocatalysts capable of anion transfer post C-H activation, offering synthetic utility.
    • Understanding the mechanisms governing these enzymes is key to expanding their synthetic applications.

    Purpose of the Study:

    • To experimentally elucidate the factors driving the bifurcation of H-atom abstraction and radical rebound in Fe(II)/α-ketoglutarate-dependent radical halogenases.
    • To identify the minimal amino acid residues responsible for the enzyme's catalytic plasticity and reaction scope.

    Main Methods:

    • Utilized experimental evidence to investigate the catalytic mechanism of Fe(II)/α-ketoglutarate-dependent radical halogenases.
    • Focused on the roles of the dynamic metal coordination sphere and second-sphere hydrogen-bond networks in reaction pathway determination.

    Main Results:

    • Provided the first experimental evidence that both a dynamic metal coordination sphere and a second-sphere hydrogen-bond network govern the bifurcation of H-atom abstraction and radical rebound.
    • Identified a minimal two-residue motif (Asn224 and Ile151) as necessary and sufficient for this process.

    Conclusions:

    • The identified minimal motif provides a new paradigm for understanding the evolution of catalytic plasticity in these enzymes.
    • Offers insights into designing novel biocatalysts with expanded reaction scopes for C-H activation and functionalization.