[Fe(F 20 TPP)Cl]‐Catalyzed Amination with Arylamines and {[Fe(F 20 TPP)(NAr)](PhINAr)} + . 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(F 20 TPP)Cl] (H 2 F 20 TPP= meso ‐tetrakis(pentafluorophenyl)porphyrin) as a catalyst. This catalytic method is applicable for both intra‐ and intermolecular amination of sp 2 and sp 3 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(F 20 TPP)(NC 6 H 4 ‐ p ‐NO 2 )](PhI=NC 6 H 4 ‐ p ‐NO 2 )}   +   .intermediate in the catalysis.