The use of a peroxidase-mimicking Fe complex has been reported on the basis of the biuret-modified TAML macrocyclic ligand framework (Fe-bTAML) as a catalyst to perform selective oxidation of unactivated 3° C-H bonds and activated 2° C-H bonds with low catalyst loading (1 mol %) and high product yield (excellent mass balance) under near-neutral conditions and broad substrate scope (18 substrates which includes arenes, heteroaromatics and polar functional groups). Aliphatic C-H oxidation of 3° and 2° sites of complex substrates was achieved with predictable selectivity using steric, electronic and stereoelectronic rules that govern site selectivity, which included oxidation of (+)-artemisinin to (+)-10$\beta$-hydroxyartemisinin. Mechanistic studies indicate FeV(O) to be the active oxidant during these reactions.