A novel biocatalytic protocol enables the direct and selective introduction of nitrogen functionalities via activation of allylic C-H bonds. Utilizing an oxidase/peroxidase couple for the formal dehydrogenation of N-hydroxycarbamates and hydroxamic acids with air as terminal oxidant, acylnitroso species are generated under particularly mild aqueous conditions. The reactive intermediates undergo C-N bond formation through an ene-type mechanism and provide high yields both in intramolecular and intermolecular enzymatic aminations. Investigations on alternative reaction pathways and labelling studies provide more insights into this unprecedented biocatalytic promiscuity of classical oxidoreductases as catalysts for nitroso ene-based transformations.
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Nitroso ESI pre