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Related Concept Videos

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 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: 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 Reactivity: Electrophilic Radicals01:02

Radical Reactivity: Electrophilic Radicals

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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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Radical Substitution: Allylic Chlorination01:31

Radical Substitution: Allylic Chlorination

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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...
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Radical Substitution: Allylic Bromination01:27

Radical Substitution: Allylic Bromination

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In organic synthesis, the formation of products can be altered by changing the reaction conditions. For example, a dibromo addition product is formed when propene is treated with bromine at room temperature. In contrast, propene undergoes allylic substitution in non-polar solvents at high temperatures to give 3-bromopropene. In order to avoid the addition reaction, the bromine concentration must be kept as low as possible throughout the reaction. This can be achieved using N-bromosuccinimide...
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Olefinic C-H functionalization through radical alkenylation.

Shan Tang1, Kun Liu, Chao Liu

  • 1College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei 430072, P. R. China. aiwenlei@whu.edu.cn.

Chemical Society Reviews
|January 3, 2015
PubMed
Summary
This summary is machine-generated.

Directly adding alkenyl groups to organic molecules is ideal. Recent advances show radical alkenylation via single-electron-transfer (SET) offers a versatile alternative to traditional methods like the Heck reaction.

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Area of Science:

  • Organic Chemistry
  • Catalysis
  • Synthetic Methodology

Background:

  • Direct olefinic C-H functionalization is a key synthetic strategy.
  • The Heck reaction is a traditional method for alkenylation but has limitations.
  • Radical pathways offer new avenues for C-H functionalization.

Purpose of the Study:

  • To review recent advances in radical alkenylation.
  • To highlight the versatility of radical addition and SET oxidation/elimination.
  • To provide an overview of emerging methods for introducing alkenyl groups.

Main Methods:

  • Radical addition to alkenes.
  • Single-electron-transfer (SET) oxidation/elimination.
  • Transition metal catalysis (implied context from Heck reaction comparison).

Main Results:

  • Radical alkenylation enables the introduction of diverse alkenyl groups.
  • This pathway overcomes limitations of traditional methods like the Heck reaction.
  • It allows functionalization with various carbon-centered and heteroatom-centered radicals.

Conclusions:

  • Radical alkenylation is a powerful and emerging strategy in organic synthesis.
  • This approach broadens the scope of C-H functionalization.
  • Further development in this field promises significant advancements in molecule synthesis.