Jove
Visualize
Contact Us
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Concept Videos

Radical Formation: Addition00:47

Radical Formation: Addition

1.6K
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...
1.6K
Radical Reactivity: Overview01:11

Radical Reactivity: Overview

2.2K
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...
2.2K
Radical Substitution: Allylic Bromination01:27

Radical Substitution: Allylic Bromination

5.2K
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...
5.2K
Radical Formation: Overview01:03

Radical Formation: Overview

1.9K
A bond can be broken either by heterolytic bond cleavage to form ions or homolytic bond cleavage to yield radicals. A fishhook arrow is used to represent the motion of a single electron in homolytic bond cleavage. There are two main sources from which radicals can be formed:
Radicals from spin-paired molecules:
Radicals can be obtained from spin-paired molecules either by homolysis or electron transfer. While two radicals are formed in the former, an electron is added in the...
1.9K
Radical Formation: Elimination00:51

Radical Formation: Elimination

1.6K
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...
1.6K
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride01:26

Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride

1.5K
Radical substitution reactions can be used to remove functional groups from molecules. The hydrogenolysis of alkyl halides is one such reaction, where the weak Sn–H bond in tributyltin hydride reacts with alkyl halides to form alkanes. Here, the reagent Bu3SnH yields tributyltin halide as a byproduct.
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation...
1.5K

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

Synthesis of 4-Alkyl-2-chloro Imidazoles Using Intermolecular Radical Additions.

Organic letters·2024
Same author

α-Amido Trifluoromethyl Xanthates: A New Class of RAFT/MADIX Agents.

Molecules (Basel, Switzerland)·2024
Same author

Short Formal Syntheses of Lycorine and Congeners Using a 5<i>-Endo-Trig</i>/6<i>-Endo-Trig</i> Radical Cyclization Sequence.

Organic letters·2024
Same author

Some Aspects of α-(Acyloxy)alkyl Radicals in Organic Synthesis.

Molecules (Basel, Switzerland)·2023
Same author

A Versatile Route to Acyl (MIDA)Boronates.

Chemistry (Weinheim an der Bergstrasse, Germany)·2023
Same author

The xanthate route to tetralones, tetralins, and naphthalenes. A brief account.

Organic & biomolecular chemistry·2023

Related Experiment Video

Updated: Apr 30, 2026

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

20.7K

A radical thia-Brook rearrangement.

Béatrice Quiclet-Sire1, Samir Z Zard

  • 1Laboratoire de Synthèse Organique, CNRS UMR 7652, Ecole Polytechnique, F-91128 Palaiseau, France. beatrice.sire@polytechnique.edu samir.zard@polytechnique.edu.

Chemical Communications (Cambridge, England)
|April 26, 2014
PubMed
Summary
This summary is machine-generated.

This study details a radical chain rearrangement in silicon compounds, where a silyl group moves from carbon to sulfur. This process utilizes readily available starting materials derived from vinylsilanes and dithiocarbonates.

More Related Videos

Utilization of Stop-flow Micro-tubing Reactors for the Development of Organic Transformations
13:09

Utilization of Stop-flow Micro-tubing Reactors for the Development of Organic Transformations

Published on: January 4, 2018

38.8K
Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
07:12

Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions

Published on: July 17, 2020

5.7K

Related Experiment Videos

Last Updated: Apr 30, 2026

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

20.7K
Utilization of Stop-flow Micro-tubing Reactors for the Development of Organic Transformations
13:09

Utilization of Stop-flow Micro-tubing Reactors for the Development of Organic Transformations

Published on: January 4, 2018

38.8K
Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
07:12

Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions

Published on: July 17, 2020

5.7K

Area of Science:

  • Organosilicon Chemistry
  • Radical Reactions

Background:

  • Geminal mercapto silanes are versatile intermediates in organic synthesis.
  • Understanding their reactivity is crucial for developing new synthetic methodologies.

Purpose of the Study:

  • To investigate the radical chain rearrangement of geminal mercapto trialkyl- and trialkoxy-silanes.
  • To elucidate the mechanism of silyl group migration from carbon to sulfur.

Main Methods:

  • Radical chain rearrangement reactions.
  • Synthesis of starting materials via peroxide-initiated radical addition of dithiocarbonates (xanthates) to vinylsilanes.

Main Results:

  • Efficient radical chain rearrangement observed in geminal mercapto silanes.
  • Successful migration of the silyl group from carbon to sulfur.
  • Readily accessible starting materials synthesized through radical addition.

Conclusions:

  • Geminal mercapto silanes undergo facile silyl group migration via a radical chain mechanism.
  • The synthetic route provides a straightforward method for preparing these rearranged silanes.