The mechanisms of O2 reduction include many types such as radical based processes, oxidative addition, insertion, and oxygenase-like. Understanding how to experimentally differentiate them and design catalysts for specific mechanisms is difficult. Most synthetic oxidations of organic substrates with homogenous catalysts and O2 are radical processes. In contrast, many transition metal dependent (di)oxygenases react with O2 and substrate through “activated” species such as superoxo, peroxo, hydroperoxo, oxido, and hydroxido. To harness the full potential of aerobic oxidations, chemists need full control of the various reaction paths available. In this presentation, new design principles are discussed that will enable access to oxygenase-like mechanisms and avoid radical-based processes.

Design principles in synthetic non-heme (di)oxygenases

2019 Fall National Meeting

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