A Unified Method for\nOxidative and Reductive Decarboxylative\nArylation with Orange Light-Driven Ir/Ni Metallaphotoredox Catalysis

Carboxylic acids and their derivatives are powerful building\nblocks\nin dual Ir/Ni metallaphotoredox methods of decarboxylative arylation\ndue to their abundance as feedstock compounds. However, the library\nof accessible carboxylic acids is limited by trends in radical stability,\noften necessitating the development of specific systems for challenging\nsubstrates. Herein, we disclose the application of a new Ir(III) photocatalyst\nand low-energy orange light Ir/Ni metallaphotoredox system with broad\napplicability in activating both native carboxylic acids and redox-active\nesters (RAEs). This method represents the first known example of complementary\noxidative and reductive decarboxylative paradigms with broadly similar\nreaction conditions, unlocking the reactivity for challenging substrates.\nWe further show a wide scope of aryl halide and acid coupling partners\nin both regimes, with added advantages over blue-light-catalyzed aryl\nalkylation for photosensitive substrates.