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
作者:Chao Che、Zhaosheng Qian、Mingchang Wu、Ying Zhao、Gangguo Zhu
DOI:10.1021/acs.joc.8b00666
日期:2018.5.18
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
描述了新型的银催化的环丙醇和环丁醇的开环酰化。反应在温和和中性的条件下进行,并以宽阔的底物范围提供了容易获得的不对称1,4-和1,5-二酮的收率。包括DFT计算在内的机理研究表明,涉及一种不常见的水助1,2-HAT工艺,该工艺强烈放热,因此促进了将碳自由基添加到醛中。与传统的还原性自由基加成方案相比,这项工作代表了将分子间氧化性自由基加成醛的第一个实例,从而为从容易获得的醛直接合成无环酮提供了新的策略。