Catalytic hydrogenation of functionalized amides under basic and neutral conditionsElectronic supplementary information (ESI) available: Experimental details and spectroscopic data are given in the supporting information. See DOI: 10.1039/c4cy01227e

A new, base-free high turnover number (TON) catalyst for hydrogenation of simple and functionalized amides is prepared by reacting [Ru(η 3 -C 3 H 5 )(Ph 2 P(CH 2 ) 2 NH 2 ) 2 ]BF 4 and BH 4 − under hydrogen. The hydrogenation proceeds with C-N cleavage to form the corresponding amine and alcohol. The base-free and base-promoted hydrogenations tolerate alcohols, amines, aromatic bromides, chlorides and fluorides, ethers, certain olefins, and N-heterocyclic rings. The reaction was used to deprotect the amine groups in certain acetyl amides to form, for example, an N-heterocyclic amine containing an aryl bromide. The base-free system also selectively hydrogenates N -acyloxazolidinones without epimerization at the α-position, and reduced β-lactams to form the corresponding amino alcohols. A new, base-free high turnover number (TON) catalyst for hydrogenation of simple and functionalized amides is prepared by reacting [Ru(η 3 -C 3 H 5 )(Ph 2 P(CH 2 ) 2 NH 2 ) 2 ]BF 4 and BH 4 − under hydrogen.