Iron-Catalyzed Hydrogenation of Amides to Alcohols and Amines

This article describes the iron-catalyzed hydrogenation of unactivated amides. Under the optimal conditions, a PNP-ligated Fe catalyst affords 25–300 turnovers of products derived from C–N bond cleavage. This reaction displays a broad substrate scope, including a variety of 2° and 3° amide substrates. The reaction progress of <i>N,N</i>-dimethylformamide hydrogenation has been monitored in situ using Raman spectroscopy. This technique enables direct comparison of the relative activity of the Fe-PNP catalyst to that of its Ru analogue. Under otherwise identical conditions, the Fe and Ru catalysts exhibit rates within a factor of 2

Rhodium Hydrogenation Catalysts Supported in Metal Organic Frameworks: Influence of the Framework on Catalytic Activity and Selectivity

The cationic rhodium complexes (dppe)­Rh­(COD)­BF₄ and (MeCN)₂Rh­(COD)­BF₄ have been supported in metal–organic frameworks bearing anionic nodes (ZJU-28) and anionic linkers (MIL-101-SO₃) via ion exchange. These MOF-supported Rh species serve as recyclable catalysts for the hydrogenation of both the terminal alkene substrate 1-octene and the internal alkene substrate 2,3-dimethylbutene. The nature of the MOF support impacts various aspects of catalysis, including: (i) the rate of 1-octene hydrogenation, (ii) the activity and recyclability of the catalyst in 2,3-dimethylbutene hydrogenation, and (iii) the size selectivity of hydrogenation with alkene substrates appended to calixarenes