One-Pot, Metal-Free Conversion of Anilines to Aryl Bromides and Iodides

A metal-free synthesis of aryl bromides and iodides from anilines via halogen abstraction from bromotrichloromethane and diiodomethane is described. This one-pot reaction affords aryl halides from the corresponding anilines in moderate to excellent yields without isolation of diazonium salts. The transformation has short reaction times, a simple workup, and insensitivity to moisture and air and avoids excess halogenation. DFT calculations support a S_RN1 mechanism. This method represents a convenient alternative to the classic Sandmeyer reaction.