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Radical Anti-Markovnikov Addition to Alkenes: Mechanism01:17

Radical Anti-Markovnikov Addition to Alkenes: Mechanism

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The reaction of hydrogen bromide with alkenes in the presence of hydroperoxides or peroxides proceeds via anti-Markovnikov addition. The radical chain reaction comprises initiation, propagation, and termination steps.
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy...
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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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Radical Anti-Markovnikov Addition to Alkenes: Overview01:25

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The addition of hydrogen bromide to alkenes in the presence of hydroperoxides or peroxides proceeds via an anti-Markovnikov pathway and yields alkyl bromides.
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Radical Reactivity: Overview01:11

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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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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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Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation02:24

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

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Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
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Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
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Alkene dialkylation by triple radical sorting.

Johnny Z Wang1, William L Lyon1, David W C MacMillan2

  • 1Merck Center for Catalysis at Princeton University, Princeton, NJ, USA.

Nature
|February 13, 2024
PubMed
Summary

Bimolecular homolytic substitution (SH2) catalysis enables selective radical sorting for C(sp3)-C(sp3) bond formation. This new method achieves alkene dialkylation by differentiating three radical species, accelerating complex molecule synthesis.

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Area of Science:

  • Organic Chemistry
  • Catalysis
  • Synthetic Methodology

Background:

  • Bimolecular homolytic substitution (SH2) catalysis has advanced cross-coupling reactions.
  • Existing SH2 methods allow selective combination of primary, secondary, or tertiary radicals.
  • A key challenge remains the simultaneous dialkylation of alkenes via radical sorting.

Purpose of the Study:

  • To develop a novel SH2 catalytic approach for alkene dialkylation.
  • To enable the simultaneous construction of two C(sp3)-C(sp3) bonds.
  • To overcome limitations of statistical radical recombination and side reactions.

Main Methods:

  • Utilizing bimolecular homolytic substitution (SH2) catalysis.
  • In situ generation of three distinct radical species.
  • Employing radical sorting based on size and electronic properties.

Main Results:

  • Achieved regioselective dialkylation of unactivated alkenes.
  • Successfully sorted electrophilic and nucleophilic radicals across alkenes.
  • Demonstrated a new pathway for forming C(sp3)-C(sp3) bonds.

Conclusions:

  • This work establishes a distinct mechanistic approach for alkene dialkylation.
  • The developed SH2 catalysis accelerates access to C(sp3)-rich molecules.
  • This methodology expands the scope of radical-based cross-coupling reactions.