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Thermal and Photochemical Electrocyclic Reactions: Overview

Thermal and Photochemical Electrocyclic Reactions: Overview

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.

Crossed Aldol Reactions: Overview

Crossed Aldol Reactions: Overview

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.

Thermal Electrocyclic Reactions: Stereochemistry

Thermal Electrocyclic Reactions: Stereochemistry

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.

Cycloaddition Reactions: Overview

Cycloaddition Reactions: Overview

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.

Photochemical Electrocyclic Reactions: Stereochemistry

Photochemical Electrocyclic Reactions: Stereochemistry

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

Pericyclic Reactions: Introduction

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...

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Updated: Jul 26, 2025

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

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

Published on: April 4, 2014

Electroreductive Cross-Electrophile Coupling (eXEC) Reactions.

Yaowen Liu¹, Pengfei Li¹, Yanwei Wang¹

¹State Key Laboratory and Institute of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, 94 Weijin Road, Tianjin, 300071, China.

Angewandte Chemie (International Ed. in English)

|June 16, 2023

Summary

This summary is machine-generated.

Electrochemistry offers a sustainable route for organic synthesis by using electrons instead of chemical reagents. Recent advances in electroreductive cross-electrophile coupling (eXEC) enable efficient C-C and C-heteroatom bond formation.

Keywords:

Alkyl Electrophiles Aryl Electrophiles Cross Coupling Electrochemistry Electroreduction

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Published on: June 21, 2017

Area of Science:

Organic Chemistry
Electrochemistry
Sustainable Synthesis

Background:

Electrochemistry provides a green alternative to traditional chemical oxidants and reductants.
The combination of electrochemistry with electrophiles is a growing method for synthesizing complex organic molecules.
This approach facilitates the formation of crucial carbon-carbon and carbon-heteroatom bonds.

Purpose of the Study:

To review recent advancements in electroreductive cross-electrophile coupling (eXEC) reactions.
To highlight the use of accessible electrophiles in these transformations.
To showcase the sustainability and efficiency of eXEC in modern organic synthesis.

Main Methods:

Systematic review of literature from the past decade.
Focus on electroreductive cross-electrophile coupling (eXEC) reactions.
Analysis of reactions involving organic (pseudo)halides and small molecules like CO2, SO2, and D2O.

Main Results:

Demonstrated the viability and increasing popularity of eXEC reactions.
Showcased the efficient construction of C-C and C-heteroatom bonds using readily available electrophiles.
Highlighted the sustainable nature of electrochemical methods in complex molecule synthesis.

Conclusions:

Electroreductive cross-electrophile coupling (eXEC) is a powerful and sustainable strategy for organic synthesis.
The methodology effectively utilizes common electrophiles for constructing challenging molecular architectures.
Continued research in eXEC promises further advancements in green chemistry and complex molecule synthesis.