[Fe(F20TPP)Cl]-Catalyzed Amination with Arylamines and {[Fe(F20TPP)(NAr)](PhI=NAr)}(+)center dot 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 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(F20TPP)(NC6H4-p-NO2)](PhI=NC6H4-p-NO2)}+. intermediate in the catalysis.