Excited-State S N Ar Reactions of Nitroarenes
Abstract
Nucleophilic aromatic substitution (S N Ar) traditionally requires ground-state dearomatization to form Meisenheimer intermediates, restricting the reactivity to arenes bearing strong electron-withdrawing groups (EWGs). Here we disclose excited-state S N Ar reactions of nitroarenes under visible light irradiation, in which triplet-state electronic reorganization furnishes a strong aromaticity-recovery driving force for C Ar –NO 2 substitution, enabling reaction pathways that are inaccessible in the ground state. Following computational evaluation of common nucleophiles, we developed a synthetically practical protocol that enables denitrative substitution across diverse polycyclic arenes. These findings demonstrate that photoexcitation can reshape the aromatic character of arenes, thereby offering a new strategy to access previously inaccessible modes of arene functionalization.
Fields of Study & Subjects
Radical Photochemical Reactions
Chemical Reactions and Mechanisms
Photochromic and Fluorescence Chemistry
Publication details
- Journal / source
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Volume
- 148
- Issue
- 14
- Pages
- 14971–14980
- Publication date
- 1 April 2026
- Language
- EN