Iron(III)-Catalyzed C-H Functionalization: ortho-Benzoyloxylation of N,N-Dialkylanilines and Its Application to 1,4-Benzoxazepines

A C-O bond-formation reaction that proceeds through C-H functionalization of N,N-dialkylanilines at the ortho-position is presented. The iron-catalyzed selective ortho-benzoyloxylation follows a polar Friedel-Crafts-like mechanism and is sensitive to the nucleophilicity of the anilines. The benzoyloxylation of a variety of N,N-disubstituted anilines and N-phenyl heterocycles is carried out under extremely mild conditions. Furthermore, the methodology has been successfully employed for the generation of 1,4-benzoxazepines and o-aminophenols.