1] Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein Straße 29a, 18059 Rostock, Germany [2].
Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein Straße 29a, 18059 Rostock, Germany.
Nat Commun. 2014 Jun 27;5:4111. doi: 10.1038/ncomms5111.
The catalytic hydrogenation of carboxylic acid derivatives represents an atom-efficient and clean reduction methodology in organic chemistry. More specifically, the selective hydrogenation of nitriles offers the possibility for a green synthesis of valuable primary amines. So far, this transformation lacks of useful, broadly applicable non-noble metal-based catalyst systems. In the present study, we describe a molecular-defined iron complex, which allows for the hydrogenation of aryl, alkyl, heterocyclic nitriles and dinitriles. By using an iron PNP pincer complex, we achieve very good functional group tolerance. Ester, ether, acetamido as well as amino substituents are not reduced in the presence of nitriles. Moreover, nitriles including an α,β-unsaturated double bond and halogenated derivatives are well tolerated in this reaction. Notably, our complex constitutes the first example of an homogeneous catalyst, which permits the selective hydrogenation of industrially important adipodinitrile to 1,6-hexamethylenediamine.
羧酸衍生物的催化氢化是有机化学中一种原子经济性和清洁的还原方法。更具体地说，腈的选择性氢化为有价值的伯胺的绿色合成提供了可能性。到目前为止，这种转化缺乏有用的、广泛适用的非贵金属基催化剂体系。在本研究中，我们描述了一种分子定义的铁配合物，它允许芳基、烷基、杂环腈和二腈的氢化。通过使用铁 PNP 钳形配合物，我们实现了非常好的官能团耐受性。酯、醚、乙酰胺基以及氨基取代基在腈的存在下不会被还原。此外，包括α,β-不饱和双键和卤代衍生物的腈在该反应中也能很好地耐受。值得注意的是，我们的配合物是首例允许工业上重要的己二腈选择性氢化生成 1,6-己二胺的均相催化剂的实例。
