A molecular electron density theory study of the [3 + 2] cycloaddition reaction of nitrones with ketenes
Mar Ríos-Gutiérrez1, Andrea Darù, Tomás Tejero
1Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, E-46100 Burjassot, Valencia, Spain. domingo@utopia.uv.es.
Abstract:
The [3 + 2] cycloaddition (32CA) reaction between nitrones and ketenes has been studied within the Molecular Electron Density Theory (MEDT) at the Density Functional Theory (DFT) MPWB1K/6-311G(d,p) computational level. Analysis of the conceptual DFT reactivity indices allows the explanation of the reactivity, and the chemo- and regioselectivity experimentally observed. The particular mechanism of this 32CA reaction involving low electrophilic ketenes has been elucidated by using a bonding evolution theory (BET) study. It is determined that this reaction takes place in one kinetic step only but in a non-concerted manner since two stages are clearly identified. Indeed, the formation of the second C-O bond begins when the first O-C bond is already formed. This study has also been applied to predict the reactivity of nitrones with highly electrophilic ketenes. Interestingly, this study predicts a switch to a two-step mechanism due to the higher polar character of this zw-type 32CA reaction. In both cases, BET supports the non-concerted nature of the 32CA reactions between nitrones and ketenes.
Related Concept Videos
Cycloaddition Reactions: Overview
Cycloaddition Reactions: MO Requirements for Thermal Activation
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Nitrosation of Enols
Cycloaddition Reactions: MO Requirements for Photochemical Activation
Conjugate Addition of Enolates: Michael Addition


![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)