A Unified Method for Oxidative and Reductive Decarboxylative Arylation with Orange Light-Driven Ir/Ni Metallaphotoredox Catalysis

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