Related Experiment Video
Updated: Aug 7, 2026
![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)
Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Theoretical calculations on the cycloreversion of oxetane radical cations
M Angeles Izquierdo1, Luis R Domingo, Miguel A Miranda
1Departamento de Química Organica/Instituto de Ciencia Molecular, Universidad de Valencia, c/Dr. Moliner 50, 64100, Valencia, Spain.
Abstract:
The molecular mechanism for the cycloreversion of oxetane radical cations has been studied at the UB3LYP/6-31G* level. Calculations support that the cycloreversion takes place via a concerted but asynchronous process, where C-C bond breaking at the transition state is more advanced than O-C breaking. This allows a favorable rearrangement of the spin electron density from the oxetane radical cation (with the spin density located mainly on the oxygen atom) to the alkene radical cation which is one of the final products. Inclusion of solvent effects does not modify the gas-phase results.
Related Concept Videos
Thermal Electrocyclic Reactions: Stereochemistry
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.
Aromatic Hydrocarbon Cations: Structural Overview
Removing one hydrogen from the intervening CH2 group with both...
Thermal and Photochemical Electrocyclic Reactions: Overview
Preparation of Epoxides
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...
Cycloaddition Reactions: Overview
Cycloaddition Reactions: MO Requirements for Thermal Activation

