Cai Yuan, Dawor Mahiob, Gaurav Gaurav, Ritter Tobias
Max-Planck-Institut für Kohlenforschung, D-45470 Mülheim an der Ruhr, Germany.
Institute of Organic Chemistry, RWTH Aachen University, 52074 Aachen, Germany.
J Am Chem Soc. 2025 Jun 4;147(22):18438-18444. doi: 10.1021/jacs.5c05699. Epub 2025 May 20.
The simultaneous construction of C-C and C-X bonds in a single step facilitates multistep synthesis through rapid carbon chain growth and subsequent transformations of halide functionalities. Traditional Kharasch addition requires simple polyhalogenated compounds or those with electron-withdrawing groups at the α-carbon. Herein, we present a Kharasch-type reaction utilizing a broad range of carboxylic acid-derived redox-active esters as the alkyl source, which enables the efficient introduction of highly functionalized alkyl groups. Our method produces α-halo carbonyls that enable versatile nucleophilic substitutions for synthesizing valuable compounds, such as unnatural α-amino acids.
在一步反应中同时构建C-C键和C-X键,通过快速的碳链增长以及随后卤化物官能团的转化,有助于多步合成。传统的卡拉施加成反应需要简单的多卤代化合物或在α-碳上带有吸电子基团的化合物。在此,我们展示了一种卡拉施型反应,该反应利用多种羧酸衍生的氧化还原活性酯作为烷基源,能够高效引入高度官能化的烷基。我们的方法生成α-卤代羰基化合物,可用于多种亲核取代反应以合成有价值的化合物,如非天然α-氨基酸。