Merging Organocatalysis and Photocatalysis: A New Momentum in Covalent Radical Catalysis

Abstract The use of free radicals as organocatalysts constitutes a powerful strategy to activate and functionalize unsaturated carbon chains. Indeed, the unique affinity of open‐shell species for alkenes and alkynes can be rerouted to achieve the catalytic covalent activation of the substrate and control a subsequent radical cascade. However, the field of covalent radical catalysis has remained challenging for decades due to important issues in terms of catalyst handling, reaction design and viability. Recently, these pitfalls have been addressed one by one by the use of photocatalysis to control the generation and the reactivity of radical catalysts. This Concept article aims to highlight recent achievements in the field of photocatalyzed covalent radical catalysis and the perspectives offered by such catalytic combinations. The reaction mechanisms and the interconnection between the catalytic cycles are reviewed with the hope of demonstrating the synthetic potential of this approach and foster a rapid growth of this nascent topic.