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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.

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.

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

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.

Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry

Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry

Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.

Diels–Alder Reaction Forming Cyclic Products: Stereochemistry

Diels–Alder Reaction Forming Cyclic Products: Stereochemistry

The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.

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Related Experiment Video

Updated: Aug 6, 2025

Solid-phase Synthesis of [4.4] Spirocyclic Oximes

Solid-phase Synthesis of [4.4] Spirocyclic Oximes

Published on: February 6, 2019

Electrochemical Dearomative Spirocyclization.

Nan Li¹, Zhaojiang Shi¹, Wei-Zhen Wang¹

¹Key Laboratory of Molecule Synthesis and, Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou, 350108, China.

Chemistry, an Asian Journal

|March 14, 2023

Summary

This summary is machine-generated.

Electrochemical dearomative spirocyclization offers a sustainable method to transform flat aromatic molecules into complex 3D spirocyclic structures. This review covers recent advancements, mechanistic insights, and synthetic uses of this powerful chemical transformation.

Keywords:

continuous-flow electrolysis dearomative electrochemistry natural products spirocyclic compounds

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Functionalized Spirocyclic Heterocycle Synthesis and Cytotoxicity Assay

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Last Updated: Aug 6, 2025

Solid-phase Synthesis of [4.4] Spirocyclic Oximes

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Published on: February 6, 2019

Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of α-Imino γ-Lactones and Alkylidene Pyrazolones

Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of α-Imino γ-Lactones and Alkylidene Pyrazolones

Published on: February 7, 2019

Functionalized Spirocyclic Heterocycle Synthesis and Cytotoxicity Assay

Functionalized Spirocyclic Heterocycle Synthesis and Cytotoxicity Assay

Published on: February 9, 2021

Area of Science:

Organic Chemistry
Green Chemistry
Synthetic Chemistry

Background:

Aromatic compounds are ubiquitous but typically flat (2D).
3D spirocyclic architectures are valuable in pharmaceuticals and materials science.
Traditional methods for creating 3D structures from 2D aromatics can be inefficient or unsustainable.

Purpose of the Study:

To review recent advancements in electrochemical dearomative spirocyclization.
To emphasize mechanistic understanding of this transformation.
To showcase the synthetic utility and applications of this methodology.

Main Methods:

Electrochemical synthesis techniques.
Dearomatization strategies.
Spirocyclization reactions.

Main Results:

Demonstration of electrochemical dearomative spirocyclization as a green and sustainable synthetic route.
Detailed mechanistic insights into the reaction pathways.
Examples of diverse 3D spirocyclic compounds synthesized from aromatic precursors.

Conclusions:

Electrochemical dearomative spirocyclization is a powerful and versatile method for accessing complex 3D molecules.
This approach offers a sustainable alternative to traditional synthetic methods.
The methodology has broad synthetic applications and potential for further development.