Zhang, LeiPfund, BjoernWenger, Oliver S.Hu, Xile2022-04-112022-04-112022-04-112022-03-1910.1002/anie.202202649https://infoscience.epfl.ch/handle/20.500.14299/187014WOS:000770633200001Oxidase-type oxidation is an attractive strategy in organic synthesis due to the use of O-2 as the terminal oxidant. Organic photocatalysis can effect metal-free oxidase chemistry. Nevertheless, current methods are limited in reaction scope, possibly due to the lack of suitable photocatalysts. Here we report an isoquinoline-derived diaryl ketone-type photocatalyst, which has much enhanced absorption of blue and visible light compared to conventional diaryl ketones. This photocatalyst enables dehydrogenative cross-coupling of heteroarenes with unactivated and activated alkanes as well as aldehydes using air as the oxidant. A wide range of heterocycles with various functional groups are suitable substrates. Transient absorption and excited-state quenching experiments point to an unconventional mechanism that involves an excited state "self-quenching" process to generate the N-radical cation form of the sensitizer, which subsequently abstracts a hydrogen atom from the alkane substrate to yield a reactive alkyl radical.Chemistry, MultidisciplinaryChemistryhydrogen atom transferminisci reactionoxidationphotocatalysisreaction mechanismshydrogen-atom transferaerobic oxidationsc(sp(3))-hcatalysisfunctionalizationarylationbondssaltstext::journal::journal article::research article