Related Experiment Video
Updated: Jan 20, 2026

Fabricating Complex Culture Substrates Using Robotic Microcontact Printing R- µCP and Sequential Nucleophilic Substitution
Published on: October 31, 2014
Are one-step aromatic nucleophilic substitutions of non-activated benzenes concerted processes?
Luis R Domingo1, Mar Ríos-Gutiérrez1, Eduardo Chamorro2
1Department of Organic Chemistry, Research Building Jeroni Muñoz, University of Valencia, Dr. Moliner 50, ESP-46100 Burjassot, Valencia, Spain. domingo@utopia.uv.es p.perez@unab.cl.
Abstract:
Aromatic nucleophilic substitution (SNAr) reactions of non-electrophilically activated benzenes have been studied within the Molecular Electron Density Theory (MEDT) at the B3LYP/6-311+G(d) computational level. These reactions, taking place through a one-step mechanism, present a high activation Gibbs free energy, ΔG≠ = 31.0 kcal mol-1, which decreases to 22.1 kcal mol-1 in the intramolecular process. A topological analysis of the electron localisation function along the reaction paths permits establishing the non-concerted nature of these SNAr reactions. A series of unstable structures, with similar electronic structures to those of Meisenheimer intermediates, are characterised. The present MEDT study makes it possible to establish that even these one-step SNAr reactions involving only two single bonds are non-concerted processes.
More Related Videos
08:12A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
05:34Efficient Synthesis of Polyfunctionalized Benzenes in Water via Persulfate-promoted Benzannulation of α,β-Unsaturated Compounds and Alkynes
Published on: December 16, 2019
Related Concept Videos
Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between...
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
Nucleophilic Aromatic Substitution: Elimination–Addition
Electrophilic Aromatic Substitution: Nitration of Benzene
Electrophilic Aromatic Substitution: Sulfonation of Benzene