Enantioselective intramolecular C-H amination catalyzed by engineered cytochrome P450 enzymes in vitro and in vivo.

Iron containing monooxygenases play diverse roles in nature, ranging from the primary metabolic functions of alkane hydroxylases to the xenobiotic detoxification and secondary metabolic roles of cytochrome P450 enzymes..[1] Common to these enzymes is the ability to reductively activate molecular oxygen to generate highly electrophilic oxygen species, whose reactivity is comparable with that of ‘oxenes’ (oxygen atoms containing six-valence electrons).[2] P450 enzymes in particular possess the remarkable ability to insert oxygen atoms at virtually any position within otherwise unreactive carbon skeletons leading to the synthesis of alcohols or epoxides in diverse natural products.