State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou, Fujian 350002, PR China.
J Am Chem Soc. 2016 May 4;138(17):5623-33. doi: 10.1021/jacs.6b01337. Epub 2016 Apr 25.
The first copper-catalyzed direct β-functionalization of saturated ketones is reported. This protocol enables diverse ketones to couple with a wide range of nitrogen, oxygen and carbon nucleophiles in generally good yields under operationally simple conditions. The detailed mechanistic studies including kinetic studies, KIE measurements, identification of reaction intermediates, EPR and UV-visible experiments were conducted, which reveal that this reaction proceeds via a novel radical-based dehydrogenation to enone and subsequent conjugate addition sequence.
首次报道了铜催化的饱和酮的直接β-官能化反应。该方案在操作简单的条件下，能够使各种酮与广泛的氮、氧和碳亲核试剂以一般良好的收率进行偶联。进行了详细的机理研究，包括动力学研究、KIE 测量、反应中间体的鉴定、EPR 和紫外-可见实验，结果表明该反应通过一种新的基于自由基的脱氢到烯酮和随后的共轭加成序列进行。
