[Fe(F20TPP)Cl]‐Catalyzed Amination with Arylamines and {[Fe(F20TPP)(NAr)](PhINAr)} + . Intermediate Assessed by High‐Resolution ESI‐MS and DFT Calculations

Amination of CH bonds catalyzed by transition metal complexes via nitrene/imide insertion is an appealing strategy for CN bond formation, and the use of iminoiodinanes, or their in situ generated forms from ‘PhI(OAc)2+primary amides (such as sulfonamides, sulfamates, and carbamates)’, as nitrogen sources for the amination reaction has been well documented. In this work, a ‘metal catalyst+PhI(OAc)2+primary arylamines’ amination protocol has been developed using [Fe(F20TPP)Cl] (H2F20TPP=meso-tetrakis(pentafluorophenyl)porphyrin) as a catalyst. This catalytic method is applicable for both intra- and intermolecular amination of sp2 and sp3 CH bonds (>27 examples), affording the amination products, including natural products such as rutaecarpine, in moderate-to-good yields. ESI-MS analysis and DFT calculations lend support for the involvement of {[Fe(F20TPP)(NC6H4-p-NO2)](PhI=NC6H4-p-NO2)} + . intermediate in the catalysis.