Figure 6.

Biomimetic aliphatic C–H oxidation and epoxidation reactivity with iron and manganese heme catalysts. (A) Reactivity and site-selectivity challenges. (B,C) The reactions are not stereospecific, leading to long-lived carbon-centered radical species that scramble stereochemistry and open cyclopropane rings. (D) Epoxidation experiments performed with stoichiometric manganese(oxo) porphyrin complexes show the presence of autoxidation products under both aerobic and anaerobic conditions, signifying an oxidant is formed with significant oxygen-centered radical character.