The Novel Radical‐Based Strategies for the Construction of α‐Allenols

α‐Allenols have become common advanced synthons for the synthesis of various of structures and are a frequent motif in natural products and pharmaceuticals. The special reactivity can occur due to the synergistic effect of the allene and hydroxy functional groups. Thus, many remarkable and elegant protocols have been explored through ionic pathways for the construction of α‐allenols. Recently, the rapid growth of radical chemistry has provided an alternative strategy to obtain α‐allenols through single‐electron transfer. As compared to the ionic pathway, the radical pathway has clear advantages, such as mild conditions, high efficiency, and excellent selectivity control. In this review, the most important contributions for the construction of α‐allenols are summarized via radical intermediates by categorizing them into different types of substrates. Additionally, mechanistic studies and synthetic challenges are highlighted.