Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK.
Science. 2016 Nov 18;354(6314):851-857. doi: 10.1126/science.aaf9621.
Methods for the synthesis and functionalization of amines are intrinsically important to a variety of chemical applications. We present a general carbon-hydrogen bond activation process that combines readily available aliphatic amines and the feedstock gas carbon monoxide to form synthetically versatile value-added amide products. The operationally straightforward palladium-catalyzed process exploits a distinct reaction pathway, wherein a sterically hindered carboxylate ligand orchestrates an amine attack on a palladium anhydride to transform aliphatic amines into β-lactams. The reaction is successful with a wide range of secondary amines and can be used as a late-stage functionalization tactic to deliver advanced, highly functionalized amine products of utility for pharmaceutical research and other areas.
胺的合成和功能化方法对于各种化学应用具有重要意义。我们提出了一种通用的碳氢键活化过程，该过程结合了易得的脂肪胺和原料气一氧化碳，形成了具有综合多功能性的增值酰胺产物。该方法通过操作简单的钯催化过程得以实现，其中一个空间位阻羧酸配体协调胺对钯酐的进攻，将脂肪胺转化为β-内酰胺。该反应适用于广泛的仲胺，可作为后期功能化策略，提供用于药物研究和其他领域的先进、高度官能化的胺产物。
