Recent Advances in Visible‐Light‐Mediated Acylation of Unsaturated Hydrocarbons

Comprehensive Summary Ketones are fundamental scaffolds in medicinal, biological, and materials science. The acylation of unsaturated hydrocarbons serves as a crucial C–C bond‐forming strategy for ketone synthesis, with radical chemistry driving recent advances in this field. Among thermal‐, electro‐mediated, and other systems, visible‐light photocatalysis distinguishes itself through mild reaction conditions, operational simplicity, and broad applicability. Visible‐light‐mediated acylation of unsaturated hydrocarbons can be categorized into three main types: (1) acyl radical‐involved reactions; (2) photo/ N ‐heterocyclic carbene (NHC) cooperative catalysis via ketyl radicals; and (3) photo/transition‐metal dual catalysis involving acyl radicals or acyl‐metal species. This review systematically summarizes the progress over the past decade in the acylation of alkenes, alkynes, allenes, 1,3‐enynes, and related unsaturated hydrocarbons, with particular emphasis on acyl precursor activation strategies and their underlying mechanisms across these three catalytic paradigms. Key Scientists KEY PLAYERS in the field of Visible‐Light‐Mediated Acylation of Unsaturated Hydrocarbons.