Metalloporphyrins are a class of versatile catalysts with the capability to functionalize saturated C–H bonds via several well-defined atom/group transfer processes, including oxene, nitrene, and carbene C–H insertions. The corresponding hydroxylation, amination, and alkylation reactions provide direct approaches for the catalytic conversion of abundant hydrocarbons into value-added functional molecules through C–O, C–N, and C–C bond formations, respectively. This tutorial review describes metalloporphyrin-based catalytic systems for the functionalization of different types of sp3 C–H bonds, both inter- and intramolecularly, including challenging primary C–H bonds. Additional features of metalloporphyrin-catalyzed C–H functionalization include unusual selectivities and high turnover numbers.
