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null (Ed.)The synthetic utility of aryl radicals has been established in the last century, however, their broad applications were hampered by ineffective generation methods. It was in the last decade, that a rapid development of various redox systems took place, thus triggering a renaissance of aryl radical chemistry. This tutorial review focuses on the start-of-the-art methods for generation of aryl radicals. Primarily, various light-induced systems, including photoredox catalysis, visible light transition metal catalysis, and chemistry of electron donor–acceptor complexes, are reviewed. The main current precursors of aryl radicals are evaluated together with the selected examples of their modern applications.more » « less
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Abstract A mild visible light‐induced palladium‐catalyzed alkyl Heck reaction of diazo compounds andN‐tosylhydrazones is reported. A broad range of vinyl arenes and heteroarenes with high functional group tolerance, as well as a range of different diazo compounds, can efficiently undergo this transformation. This method features Brønsted acid‐assisted generation of hybrid palladium C(sp3)‐centered radical intermediate, which allowed for new selective C−H functionalization protocol.more » « less
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Abstract A mild visible‐light‐induced Pd‐catalyzed intramolecular C−H arylation of amides is reported. The method operates by cleavage of a C(sp2)−O bond, leading to hybrid aryl Pd‐radical intermediates. The following 1,5‐hydrogen atom translocation, intramolecular cyclization, and rearomatization steps lead to valuable oxindole and isoindoline‐1‐one motifs. Notably, this method provides access to products with readily enolizable functional groups that are incompatible with traditional Pd‐catalyzed conditions.more » « less
