Metal‐Free Synthesis of Unsymmetrical Aryl Selenides and Tellurides via Visible Light‐Driven Activation of Arylazo Sulfones

A protocol for the visible light driven preparation of unsymmetrical (hetero)aryl selenides and tellurides is described herein. The method exploits the peculiar photoreactivity of arylazo sulfones that act as thermally stable, precursors of aryl radicals under both photocatalyst‐ and additive‐free conditions. The method developed shows an impressive versatility (more than fifty compounds isolated).