[FeIII(F20‐tpp)Cl] Is an Effective Catalyst for Nitrene Transfer Reactions and Amination of Saturated Hydrocarbons with Sulfonyl and Aryl Azides as Nitrogen Source under Thermal and Microwave‐Assisted Conditions

[Fe(III)(F(20)-tpp)Cl] (F(20)-tpp=meso-tetrakis(pentafluorophenyl)porphyrinato dianion) is an effective catalyst for imido/nitrene insertion reactions using sulfonyl and aryl azides as nitrogen source. Under thermal conditions, aziridination of aryl and alkyl alkenes (16 examples, 60-95 % yields), sulfimidation of sulfides (11 examples, 76-96 % yields), allylic amidation/amination of α-methylstyrenes (15 examples, 68-83 % yields), and amination of saturated C--H bonds including that of cycloalkanes and adamantane (eight examples, 64-80 % yields) can be accomplished by using 2 mol % [Fe(III)(F(20)-tpp)Cl] as catalyst. Under microwave irradiation conditions, the reaction time of aziridination (four examples), allylic amination (five examples), sulfimidation (two examples), and amination of saturated C--H bonds (three examples) can be reduced by up to 16-fold (24-48 versus 1.5-6 h) without significantly affecting the product yield and substrate conversion.