Regioselective Synthesis of 3-Substituted Isocoumarin-1-imines via Palladium-Catalyzed Denitrogenative Transannulation of 1,2,3-Benzotriazin-4(3H)-ones and Terminal Alkynes.

A palladium-catalyzed denitrogenative transannulation strategy to access various 3-substituted isocoumarin-1-imine frameworks using 1,2,3-benzotriazin-4(3H)-ones and terminal alkynes is described. The reaction is highly regioselective and tolerates a wide range of functional groups. The reaction is believed to proceed via a five-membered palladacycle intermediate extruding environmentally benign molecular nitrogen as a by-product. The utility of this method was showcased through the one-pot synthesis of biologically relevant 3-substituted isocoumarin scaffolds.