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

Base-Catalyzed Ring-Opening of Epoxides02:26

Base-Catalyzed Ring-Opening of Epoxides

8.8K
Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
8.8K
Acid-Catalyzed Ring-Opening of Epoxides02:24

Acid-Catalyzed Ring-Opening of Epoxides

7.2K
Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
7.2K
Preparation of Epoxides03:00

Preparation of Epoxides

7.7K
Overview
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy...
7.7K
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids02:04

Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

6.2K
Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
6.2K
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 Formation: Elimination00:51

Radical Formation: Elimination

1.7K
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...
1.7K

You might also read

Related Articles

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

Sort by
Same author

Dihydroquinazolinones by Titanocene-Catalyzed Reductive Radical Addition to Quinazolinones.

Chemistry (Weinheim an der Bergstrasse, Germany)·2026
Same author

Formation Pathways of an Electrophilic μ-1,2-Peroxo Fe<sup>III</sup>Fe<sup>III</sup> Complex: Spectroscopic Characterization and Reactivity.

Journal of the American Chemical Society·2026
Same author

Bridging Vibrations and Spins: Mode-Resolved Spin-Phonon Coupling Revealed through THz EPR/Magnetic IR Simulation.

The journal of physical chemistry. A·2026
Same author

Unraveling the Mechanism of a Co(-I)-Ga Photoreductant in the Catalytic Hydrodefluorination of Electron-Rich Fluoroarenes.

Journal of the American Chemical Society·2026
Same author

2-Substituted vs 2,9-Disubstituted Phenanthroline-Ni<sup>II</sup>-halides: Speciation Control and Structural Elucidation in Solution.

Inorganic chemistry·2025
Same author

Identification of Ti(salen) Complexes for Efficient Catalysis in Single-Electron Steps by Cyclic Voltammetry.

Angewandte Chemie (International ed. in English)·2025

Related Experiment Video

Updated: May 7, 2026

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
10:12

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

Published on: April 4, 2014

12.3K

Radical-based epoxide opening by titanocenes.

Asli Cangönül1, Maike Behlendorf, Andreas Gansäuer

  • 1Max Planck Institute for Chemical Energy Conversion , Stiftstrasse 34-36, D-45470 Mülheim an der Ruhr, Germany.

Inorganic Chemistry
|October 12, 2013
PubMed
Summary

This study reveals titanocene(III)-epoxide complexes, demonstrating inner-sphere electron transfer in epoxide ring-opening reactions. This finding explains the high regioselectivity observed in titanocene-catalyzed processes.

More Related Videos

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
06:46

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Published on: June 21, 2017

6.6K
Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
06:49

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

Published on: April 22, 2016

10.5K

Related Experiment Videos

Last Updated: May 7, 2026

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
10:12

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols

Published on: April 4, 2014

12.3K
Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
06:46

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Published on: June 21, 2017

6.6K
Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
06:49

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

Published on: April 22, 2016

10.5K

Area of Science:

  • Organometallic Chemistry
  • Reaction Mechanisms
  • Spectroscopy

Background:

  • Titanocene complexes are crucial catalysts in organic synthesis.
  • Epoxides are versatile building blocks, but their ring-opening reactions can lack regioselectivity.
  • Understanding the electronic interactions during epoxide binding is key to controlling reactivity.

Purpose of the Study:

  • To investigate the electronic interactions between 2,2-diphenyloxirane and titanocene complexes.
  • To elucidate the mechanism of epoxide ring-opening catalyzed by titanocenes.
  • To provide direct evidence for transient species involved in the catalytic cycle.

Main Methods:

  • Magnetic resonance spectroscopy (e.g., NMR) to study electronic structure.
  • Quantum chemical calculations to model reaction pathways.
  • Isotope labeling and spin-trapping techniques to detect short-lived intermediates.

Main Results:

  • Complexation of 2,2-diphenyloxirane with Cp2TiCl involves chloride dissociation, forming a titanocene(III)-epoxide species.
  • The titanocene(III)-epoxide complex is transient, indicating an exothermic ring-opening reaction.
  • Evidence for a short-lived titanocene(IV)-epoxide radical species was unequivocally demonstrated using advanced detection methods.

Conclusions:

  • The unprecedented observation of titanocene(III)-epoxide complexes provides direct evidence for inner-sphere electron transfer.
  • This electron transfer mechanism is responsible for the high regioselectivity in titanocene-catalyzed epoxide ring-opening.
  • The study deepens the understanding of catalytic cycles involving early transition metals and epoxides.