Department of Chemistry, University of Illinois, Urbana-Champaign, 600 S. Mathews, Urbana, Illinois 61801, USA.
Nat Chem. 2018 Mar;10(3):333-340. doi: 10.1038/nchem.2904. Epub 2018 Jan 1.
In recent years, the synthesis of amines and other nitrogen-containing motifs has been a major area of research in organic chemistry because they are widely represented in biologically active molecules. Current strategies rely on a multistep approach and require one reactant to be activated prior to the carbon-nitrogen bond formation. This leads to a reaction inefficiency and functional group intolerance. As such, a general approach to the synthesis of nitrogen-containing compounds from readily available and benign starting materials is highly desirable. Here we present a palladium-catalysed oxidative amination reaction in which the addition of the nitrogen occurs at the less-substituted carbon of a double bond, in what is known as anti-Markovnikov selectivity. Alkenes are shown to react with imides in the presence of a palladate catalyst to generate the terminal imide through trans-aminopalladation. Subsequently, olefin isomerization occurs to afford the thermodynamically favoured products. Both the scope of the transformation and mechanistic investigations are reported.
近年来，胺类和其他含氮结构单元的合成一直是有机化学的主要研究领域，因为它们广泛存在于具有生物活性的分子中。目前的策略依赖于多步反应，并且需要在形成碳-氮键之前激活一种反应物。这导致反应效率低下和官能团不耐受。因此，从易得且无害的起始原料合成含氮化合物的通用方法是非常需要的。在这里，我们提出了一种钯催化的氧化氨化反应，其中氮的加成发生在双键的较少取代碳上，这就是所谓的反马尔可夫尼科夫选择性。烯在钯酸盐催化剂的存在下与酰亚胺反应，通过反氨钯化生成末端酰亚胺。随后，发生烯烃异构化以生成热力学上有利的产物。报道了该转化的范围和机理研究。
