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Acid-Catalyzed Ring-Opening of Epoxides

Acid-Catalyzed Ring-Opening of Epoxides

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...

Preparation of Epoxides

Preparation of Epoxides

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 acids to...

Base-Catalyzed Ring-Opening of Epoxides

Base-Catalyzed Ring-Opening of Epoxides

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...

Structure and Nomenclature of Epoxides

Structure and Nomenclature of Epoxides

Cyclic ethers are heterocyclic compounds with an oxygen atom in the ring along with carbon atoms. They are named depending on the number of carbon atoms present in their ring system. Cyclic ethers with a three-membered ring system are called “oxirane”, four-membered ring systems as “oxetane”, five-membered ring systems as “oxolane”, and six-membered ring systems as “oxane”. The cyclic structure of these rings imposes angle strain, and this strain is more in the ring having a smaller number of...

Autoxidation of Ethers to Peroxides and Hydroperoxides

Autoxidation of Ethers to Peroxides and Hydroperoxides

Ethers represent a class of chemical compounds that become more dangerous with prolonged storage because they tend to form explosive peroxides when standing in the air. Autoxidation is the spontaneous oxidation of a compound in air. In the presence of oxygen, ethers slowly oxidize to form hydroperoxides and dialkyl peroxides.

Sharpless Epoxidation

Sharpless Epoxidation

The conversion of allylic alcohols into epoxides using the chiral catalyst was discovered by K. Barry Sharpless and is known as Sharpless epoxidation. The use of a chiral catalyst enables the formation of one enantiomer of the product in excess. This chiral catalyst is mainly a chiral complex of titanium tetraisopropoxide and tartrate ester (specific stereoisomer). The stereoisomer used in the chiral catalyst dictates the formation of the enantiomer of the product. In other words, the use of...

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Updated: Jul 18, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids

Published on: May 27, 2020

How well can new-generation density functionals describe protonated epoxides where older functionals fail?

Yan Zhao¹, Donald G Truhlar

¹Department of Chemistry and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455-0431, USA.

The Journal of Organic Chemistry

|December 30, 2006

Summary

New density functional theory (DFT) methods show improved accuracy for predicting the structures and energetics of protonated cyclic ethers, including epoxides. The M05-2X functional is recommended for these chemical systems.

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Area of Science:

Computational Chemistry
Quantum Chemistry
Organic Chemistry

Background:

Density Functional Theory (DFT) is widely used for predicting molecular structures and energetics.
Previous studies, such as Carlier et al. (2006), highlighted limitations of popular DFT functionals like B3LYP for protonated epoxides.
Protonated cyclic ethers, especially epoxides, present a challenge for accurate computational modeling due to their electronic structure.

Discussion:

This study evaluates recently developed DFT functionals for their performance on protonated cyclic ethers and epoxides.
Comparison is made against established functionals, including B3LYP, which previously showed significant inaccuracies.
The performance of various functionals is assessed for both structural predictions and energetic calculations.

Key Insights:

Several novel DFT functionals demonstrate superior accuracy compared to B3LYP and other previously tested methods.
The M05-2X functional exhibits significantly improved performance for unsymmetrical protonated epoxides.
Accurate prediction of protonated ether and epoxide structures and energetics is crucial for understanding reaction mechanisms.

Outlook:

The M05-2X functional is recommended for future computational studies involving protonated epoxides and ethers.
Further investigation into the performance of advanced DFT functionals for similar chemical systems is warranted.
Improved computational accuracy can lead to better understanding and design of chemical processes involving these species.