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Related Concept Videos

π Molecular Orbitals of the Allyl Radical01:27

π Molecular Orbitals of the Allyl Radical

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Allyl radicals are three-carbon conjugated systems. They are readily formed as intermediates in halogenation reactions of alkenes involving the addition of halogen to the allylic carbon instead of the double bond. As seen in allyl cations and anions, each of the three sp2-hybridized carbon atoms in allyl radicals has an unhybridized p orbital. These orbitals combine to give three π molecular orbitals.
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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

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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

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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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Activated manganese(IV) oxide can selectively oxidize allylic and benzylic alcohols via a radical intermediate mechanism. Primary allylic alcohols are oxidized to aldehydes, while secondary allylic alcohols yield ketones. The redox reaction of potassium permanganate with an Mn(II) salt such as manganese sulfate (under either alkaline or acidic conditions), followed by thorough drying, yields the oxidizing agent: activated MnO2. While MnO2 is insoluble in the solvents used for the reaction, the...
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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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Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
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Allylic alcohols: ideal radical allylating agents?

Laurent Debien1, Béatrice Quiclet-Sire1, Samir Z Zard1

  • 1Laboratoire de Synthèse Organique, CNRS UMR 7652, Ecole Polytechnique, 91128 Palaiseau Cedex, France.

Accounts of Chemical Research
|April 24, 2015
PubMed
Summary

This study introduces a novel metal-free radical allylation method using readily available allylic alcohols and xanthates. This approach overcomes limitations of previous methods, enabling efficient synthesis of diverse alkenes, aldehydes, and ketones, including those with α-substitution.

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Area of Science:

  • Organic Chemistry
  • Radical Chemistry
  • Synthetic Methodology

Background:

  • Traditional radical allylations often rely on organostannanes and struggle with α-substituted allylating agents due to isomerization.
  • Existing heavy-metal-free methods for radical allylation are scarce, especially those accommodating α-substitution.
  • Substrate accessibility and limitations in substitution patterns hinder broader application of current radical allylation techniques.

Purpose of the Study:

  • To develop allylic alcohols into versatile and 'ideal' radical allylating agents.
  • To establish metal-free radical allylation methods compatible with α-substituted allylating agents.
  • To enable the synthesis of alkenes, aldehydes, and ketones via homolytic C-O or C-C bond cleavage.

Main Methods:

  • Conversion of allylic alcohols into 2-fluoro-6-pyridoxy or cumyl derivatives.
  • Reaction of these derivatives with xanthates under metal-free conditions using peroxides (e.g., lauroyl peroxide or di-tert-butyl peroxide).
  • Utilizing the degenerate transfer of the xanthate group to stabilize intermediate radicals and facilitate β-scission.

Main Results:

  • Successful metal-free radical allylation using activated allylic alcohol derivatives and xanthates.
  • Demonstrated synthesis of alkenes, aldehydes, and saturated/unsaturated ketones.
  • Compatibility with α- and β-substitution on the allylating agent, a significant advancement over existing methods.

Conclusions:

  • The developed method provides a robust and versatile platform for radical allylation, overcoming key limitations of previous approaches.
  • Readily accessible starting materials and mild reaction conditions allow for broad functional group tolerance.
  • This novel technology expands the scope of radical allylation, offering efficient access to complex organic molecules.