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

Thermal Sigmatropic Reactions: Overview01:16

Thermal Sigmatropic Reactions: Overview

2.1K
Sigmatropic rearrangements are a class of pericyclic reactions in which a σ bond migrates from one part of a π system to another. These are intramolecular rearrangements where the total number of σ and π bonds remain unchanged.
Sigmatropic shifts are classified based on an order term [i, j ], where i and j indicate the number of atoms across which each end of the σ bond migrates. Below are examples of a [3,3] sigmatropic shift in...
2.1K
Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)01:20

Spin–Spin Coupling: Two-Bond Coupling (Geminal Coupling)

985
Two NMR-active nuclei bonded to a central atom can be involved in geminal or two-bond coupling. Geminal coupling is commonly seen between diastereotopic protons in chiral molecules and unsymmetrical alkenes, among others.
The central atom need not be NMR-active because its electrons are affected by the electron polarization of the spin-active atoms. However, spin information is transmitted less effectively than in one-bond coupling, and 2J values are usually weaker than 1J values. The energy of...
985
UV–Vis Spectroscopy: Molecular Electronic Transitions01:16

UV–Vis Spectroscopy: Molecular Electronic Transitions

1.4K
In Ultraviolet–Visible (UV–Vis) spectroscopy, the absorption of electromagnetic radiation is used to probe the electronic structure of molecules. This technique provides insights into molecular electronic transitions, particularly the movement of electrons between different molecular orbitals. Radiation is absorbed if the energy of the electromagnetic radiation passing through the molecule is precisely equal to the energy difference between the excited and ground states. During this...
1.4K
Valence Bond Theory02:45

Valence Bond Theory

32.0K
Overview of Valence Bond Theory
32.0K
¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

1.7K
The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
1.7K
Cycloaddition Reactions: MO Requirements for Photochemical Activation01:12

Cycloaddition Reactions: MO Requirements for Photochemical Activation

2.0K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
2.0K

You might also read

Related Articles

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

Sort by
Same author

Palladium-Catalyzed Selective Alkylation of 2-Alkynyl Allyl Ethers with Hydrazones <i>via HOME</i>-Chemistry.

Organic letters·2026
Same author

Modular synthesis of trisubstituted olefins and 1,3-dienes from renewable alcohols via ligand-enabled nickel catalysis.

Nature communications·2026
Same author

Mechanistic and Experimental Insights into Ligand-Class and Radical-Identity Effects on S<sub>H</sub>2-Mediated Radical Sorting in Nickel Catalysis.

Inorganic chemistry·2026
Same author

Precision indole skeletal editing for single-carbon replacement.

Science (New York, N.Y.)·2026
Same author

Ligand-Switched Regiodivergent Fluoroallylic Alkylation of Secondary Nitroalkanes via an Unusual Inner-Sphere Pathway.

Angewandte Chemie (International ed. in English)·2026
Same author

A General Platform for Aryl/Alkyl Radical Functionalization Enabled by Photoinduced Electron Donor-Acceptor Complex.

Organic letters·2026

Related Experiment Video

Updated: Jun 16, 2025

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
12:19

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

Published on: November 29, 2018

8.4K

Intermolecular C-C/C-N σ-bond metathesis enabled by visible light.

Rujuan Li1, Renqin Zhan1, Yatao Lang1

  • 1The State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University 222 Tianshui Road Lanzhou 730000 P. R. China zenghy@lzu.edu.cn.

Chemical Science
|August 16, 2024
PubMed
Summary

Researchers developed a new photo-induced method for sigma-bond metathesis, enabling C-C and C-N bond cross-coupling without transition metals. This approach efficiently synthesizes ketones and amides, offering a greener alternative for organic synthesis.

More Related Videos

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
09:37

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry

Published on: October 18, 2019

9.6K
Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
12:07

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes

Published on: April 1, 2013

17.1K

Related Experiment Videos

Last Updated: Jun 16, 2025

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
12:19

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

Published on: November 29, 2018

8.4K
Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
09:37

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry

Published on: October 18, 2019

9.6K
Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
12:07

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes

Published on: April 1, 2013

17.1K

Area of Science:

  • Organic Chemistry
  • Photochemistry
  • Catalysis

Background:

  • Transition-metal catalysis is established for π-bond metathesis but struggles with challenging σ-bond activation due to high bond energies.
  • Activating C-C and C-N σ-bonds for metathesis reactions remains a significant hurdle in synthetic chemistry.

Purpose of the Study:

  • To introduce a novel photo-induced strategy for C-C and C-N σ-bond metathesis.
  • To achieve cross-coupling of tertiary amines with α-diketones without transition metals or photosensitizers.

Main Methods:

  • Development of a transition-metal-free, photo-induced reaction protocol.
  • Utilizing controlled experiments, intermediate trapping, and Density Functional Theory (DFT) calculations to elucidate the reaction mechanism.

Main Results:

  • Successful cross-coupling of tertiary amines and α-diketones via C-C and C-N single bond cleavage and recombination.
  • Formation of aryl alkyl ketones and aromatic amides in good to high yields.
  • Demonstrated excellent functional group compatibility under metal- and photosensitizer-free conditions.

Conclusions:

  • The study presents a groundbreaking, metal-free photo-induced method for σ-bond metathesis.
  • The findings offer a new pathway for synthesizing valuable organic compounds, overcoming limitations of traditional catalytic methods.
  • Detailed mechanistic studies provide a fundamental understanding of this novel transformation.