Nitrosonium Ion-Catalyzed Oxidative Chlorination of Arenes
Abstract
High Resolution Image Download MS PowerPoint Slide A nitrosonium-catalyzed chlorination of electron-rich arenes has been developed, employing sodium chloride as the chlorine source, molecular oxygen as the terminal oxidant, and either nitric acid or sulfuric acid as the acid promoter. This transition-metal-free protocol proceeds in acetic acid under mild conditions (25–80 °C), affording chlorinated arenes in good to excellent yields. Substrate scope studies highlighted the roles of hydrogen bonding for methoxy-substituted benzoic acids, and the experimental results indicated the formation of H 2 O 2 as the byproduct and supported a nitrosonium ion (NO + )-catalyzed mechanism. A kinetic isotope effect (KIE) of 1.1 was observed using pentadeuteriophenyl phenyl ether, consistent with the pathway involving a Wheland intermediate.
Fields of Study & Subjects
Catalytic C–H Functionalization Methods
Oxidative Organic Chemistry Reactions
Vanadium and Halogenation Chemistry
Publication details
- Journal / source
- The Journal of Organic Chemistry
- Publisher
- American Chemical Society (ACS)
- Volume
- 91
- Issue
- 2
- Pages
- 892–903
- Publication date
- 5 January 2026
- Language
- EN