White Light‐Induced Slow Kinetics Generation of Arynes

Herein, 2‐(3‐acetyl‐3‐methyl‐1‐triazen‐1‐yl)benzoic acids are synthesized from anthranilic acids, including two new derivatives, without the use of strong bases. These compounds allow the slow and controlled generation of arynes via a white light‐induced process, which participates in [3 + 2] and [4 + 2] cycloaddition reactions, as well as in a metal‐free CN bond formation reaction. This chemistry, which tolerates sulfur‐, boron‐, and silicon‐containing compounds, is successfully performed on a scale of up to 1.5 mmol. A radical mechanism for the photogeneration of arynes is proposed based on a control reaction using TEMPO. In addition, the application of triazenylbenzoic acids is evaluated through the synthesis of a dehydroaporphine compound, which is an advanced synthetic intermediate for the synthesis of aporphine alkaloids.