59528-25-5Relevant academic research and scientific papers
Transition metal-free catalytic reduction of primary amides using an abnormal NHC based potassium complex: Integrating nucleophilicity with Lewis acidic activation
Bhunia, Mrinal,Sahoo, Sumeet Ranjan,Das, Arpan,Ahmed, Jasimuddin,Sreejyothi,Mandal, Swadhin K.
, p. 1848 - 1854 (2020/03/03)
An abnormal N-heterocyclic carbene (aNHC) based potassium complex was used as a transition metal-free catalyst for reduction of primary amides to corresponding primary amines under ambient conditions. Only 2 mol% loading of the catalyst exhibits a broad substrate scope including aromatic, aliphatic and heterocyclic primary amides with excellent functional group tolerance. This method was applicable for reduction of chiral amides and utilized for the synthesis of pharmaceutically valuable precursors on a gram scale. During mechanistic investigation, several intermediates were isolated and characterized through spectroscopic techniques and one of the catalytic intermediates was characterized through single-crystal XRD. A well-defined catalyst and isolable intermediate along with several stoichiometric experiments, in situ NMR experiments and the DFT study helped us to sketch the mechanistic pathway for this reduction process unravelling the dual role of the catalyst involving nucleophilic activation by aNHC along with Lewis acidic activation by K ions.
Rapid Continuous Ruthenium-Catalysed Transfer Hydrogenation of Aromatic Nitriles to Primary Amines
Labes, Ricardo,González-Calderón, Davir,Battilocchio, Claudio,Mateos, Carlos,Cumming, Graham R.,De Frutos, Oscar,Rincón, Juan A.,Ley, Steven V.
supporting information, p. 2855 - 2858 (2017/10/06)
A continuous flow method for the selective reduction of aromatic nitriles to the corresponding amine is reported. The method is based on a ruthenium-catalysed transfer-hydrogenation process, requires no additives, and uses isopropanol as both solvent and reducing agent. The process utilizes 1 mol% of the commercially available [Ru(p -cymene)Cl 2 ] 2, with a residence time of ca. 9 min, and a throughput of 50 mmol/h. The method was successfully applied to a range of aromatic nitriles providing the corresponding primary amines in good yields.
