Light‐Driven Single‐Electron‐Transfer Processes as an Enabling Principle in Sulfur‐ and Selenium‐Multicatalysis

: Cooperativity has become a mainstay in the context of multicatalytic reaction design. The combination of two or more catalysts that possess mechanistically distinct activation principles within a single chemical setting can enable bond constructions that would be impossible for any of the catalysts alone. An emerging subdomain within the field of multicatalysis is characterized by single-electron transfer processes that are sustained by the synergistic merger of sulfur or selenium organocatalysis with photoredox catalysis. From a synthetic viewpoint, such processes have tremendous value, as they can offer new and economic pathways for the concise assembly of complex molecular architectures. Thus, the aim of this Review is to highlight recent methodological progress made in this area and to contextualize representative transformations with the mechanistic underpinnings that enable these reactions.