Ruthenium-Catalyzed Regioselective Migratory Hydroacylation of Nonactivated Allenes with Alcohols Enabled by 1,4-Ru/H Migration

作者：Yang Wu, Zheng‐Yang Gu, Zhou-Jie Wu, Shijun Li, Jian‐Ping Ma, Yu Lan, Ji‐Bao Xia · 发表于：ACS Catalysis · 年份：2025 · DOI：10.1021/acscatal.5c06836 · 被引用次数：2 · 研究领域：Catalytic C–H Functionalization Methods、Asymmetric Hydrogenation and Catalysis、Catalytic Alkyne Reactions

1,4-Metal/hydrogen migration is a flexible strategy that not only activates remote C–H bonds but also mediates regioselective coupling reactions. We describe here an intermolecular coupling between allenes and alcohols to access β,γ-unsaturated ketones via tandem ruthenium catalysis. The reaction occurs via migratory hydroacylation of allenes with an in situ-generated aldehyde through the dehydrogenation of the alcohols. This formal dual C–H functionalization reaction enables one-step efficient synthesis of β,γ-unsaturated ketones from nonchelating alcohols using a commercially available catalyst and reagent. Unusual β-regioselectivity has been achieved with C–C coupling at the central sp -hybridized carbon of allenes. Moreover, β-regioselective migratory hydroacylation of allenes with nonchelating aldehydes has also been disclosed. The detailed mechanism has been proposed based on the control experimental and computational studies involving hydrogen transfer catalysis and key 1,4-ruthenium hydrogen migration.