Modular Synthesis of ortho‐Thiolated Aryl Esters Enabled with Thiocarbonate through Catellani Strategy

Abstract Herein, we report a palladium/norbornene/copper co‐catalyzed single‐step approach that merges selective ortho C−H bond esterification with ipso thiolation for construction of synthetically versatile 2‐arylthio aryl esters under exceptionally mild conditions. Importantly, this process proceeded in a highly efficient manner, allowing alkoxycarbonyl and thio groups to be installed into one aryl iodides simultaneously by harnessing thiocarbonate as bifunctional reagent. The method has been demonstrated to accommodate good functionalities and features broad substrate scope.