Visible-Light-Induced Phosgenation Reaction of Amines by Oxygenation of Chloroform Using Chlorine Dioxide

Carbamoyl chloride supports modern society as a building block for pharmaceuticals, agrochemicals, and polymers. Although carbamoyl chlorides are generally synthesized via the reaction of amines with phosgene (COCl2), these applications of COCl2 have recently been avoided because of its high toxicity. Herein, we report the visible-light-induced in-situ preparation of COCl2 through the oxygenation of chloroform in the presence of chlorine dioxide, which leads to the safe constructions of carbamoyl chlorides with good-to-high yields and wide substrate scopes. In addition, this method can also be applied to the synthesis of various carbonates that are the starting materials for resins such as polycarbonates and polyurethanes.