3 years ago

Anti-Markovnikov alkene oxidation by metal-oxo-mediated enzyme catalysis

Ella Watkins, Hannah Minges, Grzegorz Kubik, Shan Huang, Frances H. Arnold, Stephan C. Hammer

Catalytic anti-Markovnikov oxidation of alkene feedstocks could simplify synthetic routes to many important molecules and solve a long-standing challenge in chemistry. Here we report the engineering of a cytochrome P450 enzyme by directed evolution to catalyze metal-oxo–mediated anti-Markovnikov oxidation of styrenes with high efficiency. The enzyme uses dioxygen as the terminal oxidant and achieves selectivity for anti-Markovnikov oxidation over the kinetically favored alkene epoxidation by trapping high-energy intermediates and catalyzing an oxo transfer, including an enantioselective 1,2-hydride migration. The anti-Markovnikov oxygenase can be combined with other catalysts in synthetic metabolic pathways to access a variety of challenging anti-Markovnikov functionalization reactions.

Publisher URL: http://science.sciencemag.org/cgi/content/short/358/6360/215

DOI: 10.1126/science.aao1482

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