The Novel Radical‐Based Strategies for the Synthesis of Homopropargylic Alcohols via Photochemically Driven Reactions

Homopropargylic alcohols have emerged as privileged synthetic intermediates for accessing diverse molecular architectures and are recurrent structural motifs in natural products and pharmaceuticals. Their distinctive reactivity stems from the synergistic interplay between the alkyne and hydroxyl functional groups. While numerous elegant methodologies have been developed for their synthesis via conventional two‐electron ionic pathways, the recent rise of radical chemistry via photochemically driven transformations has opened an alternative avenue to access these valuable scaffolds through single‐electron transfer processes. Compared to classical ionic approaches, the photocatalyzed radical route offers significant advantages, including milder reaction conditions, enhanced efficiency, and superior control over selectivity. In this review, we summarize key advances in the photocatalyzed radical‐based synthesis of homopropargylic alcohols, organizing the discussion according to different catalytic systems. Mechanistic insights and ongoing synthetic challenges are also critically discussed.