We present a nickel-catalyzed regioselective radical diacylation of allenes with ketoacids to produce 1,4-dione products by dual photoredox and nickel catalysis. This integrated approach merges redox-active oxidative addition and reductive elimination steps with migratory insertion. The acyl radical generated in the photoredox cycle sequentially adds to Ni(I) and Ni(II) intermediates following a Ni(I)–Ni(II)–Ni(II)–Ni(III)–Ni(I) catalytic cycle. This methodology, supported by DFT calculations, demonstrates the potential of nickel catalysis in the creation of complex molecular architectures.

中文翻译：

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区域选择性二酰化中的双重光氧化还原和镍催化：探索镍氧化态在丙二烯活化中的多功能性

我们提出了一种镍催化的丙二烯与酮酸的区域选择性自由基二酰化反应，通过双重光氧化还原和镍催化生产 1,4-二酮产品。这种集成方法将氧化还原活性的氧化加成和还原消除步骤与迁移插入结合起来。光氧化还原循环中产生的酰基自由基在 Ni(I)-Ni(II)-Ni(II)-Ni(III)-Ni(I) 催化循环后依次添加到 Ni(I) 和 Ni(II) 中间体。这种由 DFT 计算支持的方法证明了镍催化在创建复杂分子结构方面的潜力。