Abstract
The Matsuda‐Heck reaction, usually performed with palladium catalysts, can be carried out under transition‐metal‐free conditions in the presence of a KOtBu/DMF couple. This system allows the selective and direct synthesis of stilbenes from aryldiazonium salts under mild temperature (20 °C). Mechanistic studies suggest a radical pathway in which the DMF acts as the initiator of the overall process.