Selective Iron-Catalyzed N-Formylation of Amines using Dihydrogen and Carbon Dioxide,ACS Catalysis

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Selective Iron-Catalyzed N-Formylation of Amines using Dihydrogen and Carbon Dioxide
ACS Catalysis ( IF 11.3 ) Pub Date : 2018-01-19 00:00:00 , DOI: 10.1021/acscatal.7b03834
Upul Jayarathne ₁ , Nilay Hazari ₂ , Wesley H. Bernskoetter ₁

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A family of iron(II) carbonyl hydride species supported by PNP pincer ligands was identified as highly productive catalysts for the N-formylation of amines via CO₂ hydrogenation. Specifically, iron complexes supported by two different types of PNP ligands were examined for formamide production. Complexes containing a PNP ligand with a tertiary amine afforded superior turnover numbers in comparison to complexes containing a bifunctional PNP ligand with a secondary amine, indicating that bifunctional motifs are not required for catalysis. Systems incorporating a tertiary amine containing a PNP ligand were active for the N-formylation of a variety of amine substrates, achieving TONs up to 8900 and conversions as high as 92%. Mechanistic experiments suggest that N-formylation occurs via an initial, reversible reduction of CO₂ to ammonium formate followed by dehydration to produce formamide. Several intermediates relevant to this reaction pathway, as well as iron-containing deactivation species, were isolated and characterized.

中文翻译：

使用二氢和二氧化碳选择性地催化铁催化的胺的N甲酰化

由PNP钳形配体支撑的铁（II）羰基氢化物族被确定为通过CO ₂加氢使胺N-甲酰化的高产催化剂。具体而言，检查了由两种不同类型的PNP配体支撑的铁络合物的甲酰胺生成情况。与含有双功能PNP配体和仲胺的配合物相比，含有PNP配体和叔胺的配合物提供了更高的周转率，这表明催化不需要双功能的基序。包含含有PNP配体的叔胺的系统对多种胺底物的N-甲酰化反应具有活性，可实现TONs高达8900，转化率高达92％。力学实验表明N-甲酰化是通过将CO ₂最初可逆地还原为甲酸铵，然后脱水生成甲酰胺而发生的。分离并表征了与该反应途径有关的几种中间体以及含铁的钝化物质。

更新日期：2018-01-19

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