Tambe Shrikant D, Hwang Ho Seong, Park Eunhui, Cho Eun Jin
Department of Chemistry, Chung-Ang University, 84 Heukseok-ro, Dongjak-gu, Seoul 06974, Republic of Korea.
Org Lett. 2024 May 17;26(19):4147-4151. doi: 10.1021/acs.orglett.4c01373. Epub 2024 May 9.
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.
我们报道了一种镍催化的丙二烯与酮酸的区域选择性自由基双酰化反应，通过双光氧化还原和镍催化生成1,4 - 二酮产物。这种综合方法将具有氧化还原活性的氧化加成和还原消除步骤与迁移插入相结合。光氧化还原循环中产生的酰基自由基按照Ni(I)-Ni(II)-Ni(II)-Ni(III)-Ni(I)催化循环依次加成到Ni(I)和Ni(II)中间体上。该方法在DFT计算的支持下，展示了镍催化在构建复杂分子结构方面的潜力。
