Jaeger, ChristinaGregori, Bernhard J.Aho, Juhana A. S.Hallamaa, MarleenDeska, Jan2024-03-072024-03-072023-04-24Jaeger, C, Gregori, B J, Aho, J A S, Hallamaa, M & Deska, J 2023, 'Peroxidase-induced C-N bond formation via nitroso ene and Diels-Alder reactions', Green Chemistry, vol. 25, no. 8, pp. 3166-3174. https://doi.org/10.1039/d2gc04827bORCID: /0009-0005-3915-911X/work/191082885http://hdl.handle.net/10138/572688The formation of new carbon-nitrogen bonds is indisputably one of the most important tasks in synthetic organic chemistry. Here, nitroso compounds offer a highly interesting reactivity that complements traditional amination strategies, allowing for the introduction of nitrogen functionalities via ene-type reactions or Diels-Alder cycloadditions. In this study, we highlight the potential of horseradish peroxidase as biological mediator for the generation of reactive nitroso species under environmentally benign conditions. Exploiting a non-natural peroxidase reactivity, in combination with glucose oxidase as oxygen-activating biocatalyst, aerobic activation of a broad range of N-hydroxycarbamates and hydroxamic acids is achieved. Thus both intra- and intermolecular nitroso-ene as well as nitroso-Diels-Alder reactions are performed with high efficiency. Relying on a commercial and robust enzyme system, the aqueous catalyst solution can be recycled over numerous reaction cycles without significant loss of activity. Overall, this green and scalable C-N bond-forming strategy enables the production of allylic amides and various N-heterocyclic building blocks utilizing only air and glucose as sacrificial reagents.9engcc_byinfo:eu-repo/semantics/openAccessCatalyzed aerobic oxidationDerivativesEfficientRouteGreenMildAcidToolChemical sciencesArticleopenAccess9d3e94be-5a81-4576-842e-729674628f783711376385152100959000968057200001