M[TPP]Cl (M = Fe or Mn)-Catalyzed Oxidative Amination of Phenols by Primary and Secondary Anilines

Iron- and manganese-catalyzed para-selective oxidative amination of (4-R)­phenols by primary and secondary anilines was developed. Depending on the identity of the R group, the products of this efficient reaction are either benzoquinone anils (C–N coupling) that are produced via a sequential oxidative amination/dehydrogenation (R = H), oxidative amination/elimination (R = OMe) steps, or N,O-biaryl compounds (C–C coupling) that are formed when R = alkyl through an oxidative amination/[3,3]-sigmatropic rearrangement (quinamine rearrangement) process.