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Related Concept Videos

Radical Autoxidation01:20

Radical Autoxidation

The oxidation of an organic compound in the presence of air or oxygen is called autoxidation. For example, cumene reacts with oxygen to form hydroperoxide. Autoxidation involves initiation, propagation, and termination steps. Many organic compounds are susceptible to autoxidation—especially ethers in the presence of oxygen, which form hydroperoxides. Even though this reaction is slow, old ether bottles contain small amounts of peroxide, which leads to laboratory explosions during ether...
Radical Reactivity: Overview01:11

Radical Reactivity: Overview

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 molecule. These three...
Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

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 carbon–halogen...
Radical Formation: Elimination00:51

Radical Formation: Elimination

Another method of radical formation is the elimination process. It is the opposite of the addition route and is driven by the instability of the radical. For example, as depicted in Figure 1, dibenzoyl peroxide yields a pair of unstable radicals upon homolysis. Given its instability, this radical spontaneously undergoes elimination via a C–C bond cleavage to form a relatively more stable phenyl radical. The mechanism involves cleavage of the bond between the α and β positions with respect to...
Pericyclic Reactions: Introduction01:17

Pericyclic Reactions: Introduction

Pericyclic reactions are organic reactions that occur via a concerted mechanism without generating any intermediates. The reactions proceed through the movement of electrons in a closed loop to form a cyclic transition state, where rearrangement of the σ and π bonds yields specific products.
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic rearrangements are...
Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this species into the...

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Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development
14:22

Free Radicals in Chemical Biology: from Chemical Behavior to Biomarker Development

Published on: April 15, 2013

Self-terminating, oxidative radical cyclizations.

Tim Dreessen1, Christian Jargstorff, Lars Lietzau

  • 1Institut für Organische Chemie, Universität Kiel, Olshausenstr, 40, 24098 Kiel, Germany.

Molecules (Basel, Switzerland)
|November 17, 2007
PubMed
Summary

A new method converts alkynes to carbonyl compounds using self-terminating, oxidative radical cyclizations. This process employs mild conditions and O-centered radicals for efficient synthesis.

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Area of Science:

  • Organic Chemistry
  • Synthetic Chemistry

Background:

  • Oxidative cyclizations are crucial transformations in organic synthesis.
  • Developing mild and efficient methods for functionalizing alkynes remains an active area of research.

Purpose of the Study:

  • To describe a novel self-terminating, oxidative radical cyclization strategy.
  • To demonstrate the conversion of alkynes into carbonyl compounds under mild conditions.

Main Methods:

  • Utilizing O-centered inorganic and organic radicals as oxidants.
  • Employing self-terminating radical cyclization mechanisms.

Main Results:

  • Successful conversion of alkynes to carbonyl compounds.
  • Reaction proceeds under very mild conditions.
  • Demonstration of a novel synthetic pathway.

Conclusions:

  • The described method offers a new, mild approach for synthesizing carbonyl compounds from alkynes.
  • Self-terminating oxidative radical cyclizations represent a valuable addition to synthetic organic chemistry toolkits.