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How Does Nucleophilic Aromatic Substitution Really Proceed in Nitroarenes? Computational Prediction and Experimental Verification

Author:
Błaziak, Kacper, Danikiewicz, Witold, Mąkosza, Mieczysław
Source:
Journal of the American Chemical Society 2016 v.138 no.23 pp. 7276-7281
ISSN:
1520-5126
Subject:
carbon, prediction
Abstract:
The aim of this paper is to present a correct and complete mechanistic picture of nucleophilic substitution in nitroarenes based on the results obtained by theoretical calculations and experimental observations coming from numerous publications, reviews, and monographs. This work gives the theoretical background to the very well documented experimentally yet still ignored observations that the addition of nucleophiles to halo nitroarenes resulting in the formation of σᴴ adducts, which under proper reaction conditions can be transformed into the product of the SNArH reaction, is faster than the competing process of addition to the carbon atom bearing a nucleofugal group (usually a halogen atom) resulting in the “classic” SNAr reaction. Only when the σᴴ adduct cannot be transformed into the SNArH reaction product, SNAr reaction is observed.
Agid:
5418966