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The title to a seminar presentation by IC Gunsalus in 1973 was “Oxygen: An essential toxin”, referring to the complex role that atmospheric dioxygen has in biology. The relatively simple function as terminal oxidant for aerobic life was dramatically augmented by Osamu Hayaishi with his identification of an enzyme that catalyzes the conversion of catechol to muconic acid by oxidative cleavage. 1 He named this biological catalyst “pyrocatechase”, which proved to be the landmark discovery of an enzyme that incorporated atmospheric dioxygen into the carbon chain of the substrate, thereby initiating cleavage of the benzene ring. This review of the oxygenase cytochrome P450 is dedicated to Dr. Hayaishi and his pioneering discovery in what is now the 50th anniversary of his work! We now realize that Nature has found many ways to utilize atmospheric dioxygen to functionalize molecules through the use of a diverse …