Photoinduced Synthesis of <i>S</i> -Aryl Dithiocarbamates and Arylamides via Denitrogenation and CS ₂ /CO Insertion of Aryltriazenes

The targeted and selective replacement of multiple atoms in a molecule represents a robust strategy for the rapid interconversion of molecular scaffolds. Herein, an efficient strategic atom replacement strategy for synthesizing S -aryl dithiocarbamates and arylamides via photoinduced denitrogenation and CS 2 /CO insertion of aryltriazenes has been developed. In this method, aryltriazenes serve as bifunctional reagents that simultaneously provide aryl and amino groups. Upon irradiation with a purple LED, a sequence of photopromoted decomposition of nitrogen-releasing aryltriazenes and three-component coupling of CS 2, amine, and aryl radical was achieved to afford a series of S -aryl dithiocarbamates. Furthermore, arylamides can be obtained via the palladium-catalyzed azo to CO transmutation of aryltriazenes with CO under purple LED irradiation. This protocol exhibits prominent advantages such as simple operation, mild reaction conditions, readily available reagents, high atom economy, and good functional group tolerance.