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Related Concept Videos

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

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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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Radical Reactivity: Overview01:11

Radical Reactivity: Overview

2.8K
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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π Molecular Orbitals of the Allyl Radical01:27

π Molecular Orbitals of the Allyl Radical

4.6K
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.
The allyl systems have identical molecular orbitals but differ in the number of π electrons....
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Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

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Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
2.2K
Radical Formation: Addition00:47

Radical Formation: Addition

2.3K
Radicals can be formed by adding a radical to a spin-paired molecule. This is typically observed with unsaturated species, where the addition of a radical across the π bond leads to the production of a new radical by dissolving the π bond. For example, the addition of a Br radical to an alkene yields a carbon-centered radical.
Similar to charge conservation in chemical reactions, spin conservation is implicit for radical reactions. Accordingly, the product formed must possess an...
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DPPF-Catalyzed Atom-Transfer Radical Cyclization via Allylic Radical.

Longlei Hou1, Zhaozhao Zhou2, Dong Wang2

  • 1Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science and Technology , 130 Meilong Road, Shanghai 200237, China.

Organic Letters
|November 14, 2017
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Summary

This study introduces a novel iron-catalyzed atom-transfer radical cyclization (ATRC) method for allylic halides. The approach efficiently generates allylic radicals using 1,1′-bis(diphenylphosphino)ferrocene (DPPF) and single-electron transfer (SET).

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Area of Science:

  • Organic Chemistry
  • Catalysis
  • Radical Reactions

Background:

  • Atom-transfer radical cyclization (ATRC) is a powerful synthetic tool.
  • Developing efficient catalytic systems for ATRC remains an active area of research.
  • Iron catalysis offers a cost-effective and sustainable alternative to precious metal catalysts.

Purpose of the Study:

  • To report a general iron-catalyzed strategy for ATRC of allylic halides.
  • To demonstrate the utility of 1,1′-bis(diphenylphosphino)ferrocene (DPPF) as a key catalyst component.
  • To explore the application of this methodology to propargyl chlorides.

Main Methods:

  • Iron-catalyzed ATRC reactions.
  • Utilizing 1,1′-bis(diphenylphosphino)ferrocene (DPPF) as a ligand.
  • Employing single-electron transfer (SET) for radical generation.
  • Investigating reactions with allylic halides and propargyl chlorides.

Main Results:

  • Successful development of a general iron-catalyzed ATRC strategy.
  • DPPF enables efficient generation of allylic radical species via SET.
  • Demonstrated feasibility of ATRC for propargyl chlorides.
  • Obtained products containing an exocyclic allene moiety.

Conclusions:

  • The reported iron-DPPF system provides an efficient method for ATRC.
  • This strategy expands the scope of ATRC to include propargyl chlorides.
  • The methodology offers a new route to valuable organic compounds.