Figure 4.

A cytochrome P450 anti‐Markovnikov oxygenase.12 A) Competing reaction pathways for P450‐catalyzed oxo transfer to alkenes. The concerted epoxidation pathway is favored over the stepwise anti‐Markovnikov oxidation consisting of oxo transfer followed by an (enantioselective) 1,2‐hydride migration. B) Ten rounds of directed evolution accumulated 12 amino acid mutations, many of which are distant from the active site. C) aMOx can be combined with established (bio)catalysts for various challenging anti‐Markovnikov alkene functionalization reactions.