Palladium-CatalyzedInsertion of Allenes into DithioacetalsTo Access 1,3-Dithioethers

Great efforts have been devoted to synthesizing dithioethers due to their unique pharmaceutical properties. While significant success has been achieved in the synthesis of 1,1-dithioethers and 1,2-dithioethers, a concise and efficient strategy for the direct construction of 1,3-dithioethers has not yet been established. Herein, we developed a palladium-catalyzed thiomethylthiolation of allenes with dithioacetals to access a wide range of 1,3-dithioethers through the simultaneous construction of one carbon–carbon bond and one carbon–sulfur bond. A dithioacetal-coordinated cationic palladium complex was isolated and characterized, which was considered the crucial intermediate for this palladium-catalyzed transformation.