Related Experiment Video
Updated: Jun 6, 2025
09:06
Efficient and Site-specific Antibody Labeling by Strain-promoted Azide-alkyne Cycloaddition
Published on: December 23, 2016
20.8K
Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis
Lauren E Ehehalt1, Omar M Beleh1, Isabella C Priest1
1Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States.
Chemical Reviews
|November 26, 2024
Summary
This review details cross-electrophile coupling (XEC), a method for joining two different σ-electrophiles using catalyst reduction. It covers synthetic strategies, mechanistic insights, and applications up to mid-2023.
Area of Science:
- Organic Chemistry
- Catalysis
- Synthetic Methodology
Background:
- Cross-electrophile coupling (XEC) involves joining two distinct σ-electrophiles, driven by catalyst reduction.
- The field has experienced significant advancements, necessitating a comprehensive review of its progress.
- Understanding the mechanistic underpinnings is crucial for further development.
Purpose of the Study:
- To provide a comprehensive summary of cross-electrophile coupling (XEC) from its inception to mid-2023.
- To consolidate information on synthetic methods, mechanistic understanding, and applications of XEC.
- To serve as a reference for researchers exploring XEC in organic synthesis.
Main Methods:
- Review of synthetic methods categorized by bond type formed (e.g., C(sp3)-C(sp3), C(sp2)-C(sp2)).
- Analysis of mechanistic pathways for various XEC reactions.
- Compilation of data on catalysts, ligands, additives, and reductants used in XEC.
Main Results:
- Detailed coverage of C-C and C-heteroatom bond formation via XEC.
- Inclusion of chapters on alkene and alkyne difunctionalization reactions.
- Discussion of methodological developments and synthetic applications, supported by figures and notes.
Conclusions:
- XEC is a rapidly advancing area with broad applicability in synthesis.
- Optimal reaction conditions (catalysts, ligands, additives, reductants) are still evolving.
- The review compiles extensive data to reflect the current state and future potential of XEC.
More Related Videos
Related Concept Videos
01:26Thermal and Photochemical Electrocyclic Reactions: Overview
2.3K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
2.3K
01:16Cycloaddition Reactions: Overview
2.5K
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
2.5K
01:17Thermal Electrocyclic Reactions: Stereochemistry
2.0K
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
2.0K
01:26Photochemical Electrocyclic Reactions: Stereochemistry
1.8K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
1.8K
01:04Crossed Aldol Reactions: Overview
5.3K
Crossed aldol addition is the reaction between two different carbonyl compounds under acidic or basic conditions. Here, both the carbonyl compounds function as nucleophiles and electrophiles. As shown in Figure 1, such a reaction yields a mixture of products, two of which are formed via self-condensation, while the remaining two are formed via crossed-condensation. Without adjustment, the reaction's usefulness in organic chemistry is decreased.
5.3K
01:17Pericyclic Reactions: Introduction
8.2K
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...
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic...
8.2K