Carbon Dioxide Activation Center (CADIAC), Department of Chemistry and the Interdisciplinary Nanoscience Center (iNANO), Aarhus University, Gustav Wieds Vej 14, 8000, Aarhus C, Denmark.
Angew Chem Int Ed Engl. 2018 Jan 15;57(3):800-804. doi: 10.1002/anie.201710089. Epub 2017 Dec 18.
An efficient catalytic protocol for the three-component assembly of benzyl bromides, carbon monoxide, and alkyl zinc reagents to give benzyl alkyl ketones is described, and represents the first nickel-catalyzed carbonylative coupling of two sp -carbon fragments. The method, which relies on the application of nickel complexed with an NN -type pincer ligand and a controlled release of CO gas from a solid precursor, works well with a range of benzylic bromides. Mechanistic studies suggest the intermediacy of carbon-centered radicals.
描述了一种高效的催化三组分反应体系,可将苄基溴化物、一氧化碳和烷基锌试剂组装成苄基烷基酮,这代表了首例镍催化的两个 sp 碳片段的羰基偶联反应。该方法依赖于镍配合 NN 型钳形配体和从固体前体制备中释放 CO 气体的控制,适用于一系列苄基溴化物。机理研究表明其涉及到碳中心自由基的中间产物。