Transition‐Metal‐Free, General Construction of Thioamides from Chlorohydrocarbon, Amide and Elemental Sulfur

Abstract A general method for one‐pot synthesis of thioamides is developed through a three‐component reaction involving chlorohydrocarbon, amide and elemental sulfur. Such a strategy does not only avoid residual transition metal in the product but also prevent the generation of C−N coupling by‐product. The latter is prone to be generated when alkane halide and amine are present. With the protocol proposed in this work, both alkyl and aryl thioamides can be obtained in moderate to excellent yields with a high tolerance of various functional groups. External oxidants are not required in the reaction. In addition, the reaction mechanisms are addressed using a combination of controlling experiments and quantum chemical calculations.