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Efficient Synthesis of Amines by Iron‐Catalyzed C=N Transfer Hydrogenation and C=O Reductive Amination
Advanced Synthesis & Catalysis ( IF 5.4 ) Pub Date : 2018-01-12 , DOI: 10.1002/adsc.201701316
Sofia Vailati Facchini 1 , Mattia Cettolin 2 , Xishan Bai 2 , Giuseppe Casamassima 2 , Luca Pignataro 2 , Cesare Gennari 2 , Umberto Piarulli 1
Affiliation  

Here we report the catalytic transfer hydrogenation (CTH) of non‐activated imines promoted by a Fe‐catalyst in the absence of Lewis acid co‐catalysts. Use of the (cyclopentadienone)iron complex 1, which is much more active than the classical ‘Knölker complex’ 2, allowed to reduce a number of N‐aryl and N‐alkyl imines in very good yields using iPrOH as hydrogen source. The reaction proceeds with relatively low catalyst loading (0.5–2 mol%) and, remarkably, its scope includes also ketimines, whose reduction with a Fe‐complex as the only catalyst has little precedents. Based on this methodology, we developed a one‐pot CTH protocol for the reductive amination of aldehydes/ketones, which provides access to secondary amines in high yield without the need to isolate imine intermediates.

中文翻译:

铁催化的C = N转移加氢和C = O还原胺化反应可高效合成胺

在这里,我们报道了在没有路易斯酸助催化剂的情况下,由铁催化剂促进的未活化亚胺的催化转移氢化(CTH)。(环戊二烯酮)铁络合物1的使用比经典的“克诺尔克络合物” 2活性高得多,使用i可以很好地减少N-芳基和N-烷基亚胺的数量。PrOH作为氢源。该反应以相对较低的催化剂负载量(0.5–2 mol%)进行,并且值得注意的是,它的范围还包括酮亚胺,其仅以铁络合物作为唯一的催化剂还原的先例很少。基于这种方法,我们开发了一种单罐CTH方案,用于醛/酮的还原胺化,无需分离亚胺中间体,即可以高收率获得仲胺。
更新日期:2018-01-12
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