Intermolecular Oxidative Radical Addition to Aromatic Aldehydes: Direct Access to 1,4-and 1,5-Diketones via Silver-Catalyzed Ring-Opening Acylation of Cyclopropanols and Cyclobutanols
Intermolecular Oxidative Radical Addition to Aromatic Aldehydes: Direct Access to 1,4-and 1,5-Diketones via Silver-Catalyzed Ring-Opening Acylation of Cyclopropanols and Cyclobutanols
复制标题
芳香醛的分子间氧化自由基加成：通过银催化环丙醇和环丁醇的开环酰化直接生成 1,4-和 1,5-二酮
DOI：
10.1021/acs.joc.8b00666
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发表时间：
2018-05-18
影响因子：
3.6
通讯作者：
Zhu, Gangguo
中科院分区：
文献类型：
--
作者：
Che, Chao;Qian, Zhaosheng;Zhu, Gangguo
报道了一种新型的银催化环丙醇和环丁醇开环酰化反应。该反应在温和的中性条件下进行，并提供了一个方便的途径，以有希望的产率和广泛的底物范围的非对称的1，4-和1，5-二酮。包括DFT计算在内的机理研究表明，参与了一个不常见的水辅助的1，2-HAT过程，这是强烈的放热，从而促进了碳自由基添加到醛。与传统的还原性自由基加成方法相比，本研究首次提出了分子间氧化自由基加成到醛上的方法，为从容易获得的醛直接合成无环酮提供了一种新的策略。
A novel silver-catalyzed ring-opening acylation of cyclopropanols and cyclobutanols is described. The reaction proceeds under mild and neutral conditions and provides a facile access to nonsymmetric 1,4- and 1,5-diketones in promising yields with broad substrate scope. Mechanistic studies including DFT calculations suggest the involvement of an uncommon water-assisted 1,2-HAT process, which is strongly exothermic and thus promotes addition of carbon radicals to aldehydes. In contrast to traditional reductive radical addition protocols, this work represents the first example of the intermolecular oxidative radical addition to aldehydes, thus offering a novel strategy for the direct synthesis of acyclic ketones from readily accessible aldehydes.