Metal‐Free Desulfonylative and C‐H Halogenation of Arenes: A Novel Approach for Haloarene Synthesis

Abstract We report a novel metal‐free approach for the desulfonylative halogenation of aryl sulfonyl chlorides and the C‐H halogenation of arenes. This strategy employs hypervalent iodine(III) as both an oxidant and a group transfer agent with tetrabutylammonium halides (TBAX) as a halide source. The method offers several key benefits, including the use of inexpensive and readily available reagents, simple reaction conditions, compatibility with air, and the absence of transition metals.