A Scrutiny on the Reductive Amination of Carbonyl Compounds Catalyzed by Homogeneous Rh(I) Diphosphane Complexes

Abstract

The reductive amination of a series of aldehydes with secondary amines and H2 in the presence of a homogeneous Rh-diphosphane catalyst was studied in order to establish a general mechanism of this reaction and to identify conditions for the improvement of the amine/alcohol ratio in the product. Several possible intermediates as constituents of changing equilibria like half-aminals, N,O-acetals and aminals were observed in the reaction mixture by means of 1H NMR spectroscopy. In individual trials, these compounds could be successfully hydrogenated under the conditions applied for reductive amination (50 bar H2 pressure, MeOH). Some evidence is accumulated that half-aminals and N,O-acetals might be key intermediates of the reductive amination. Moreover, it was found that the formation of the undesired product alcohol is likely based on the reduction of the starting carbonyl compound. However, due to numerous equilibria consisting of several intermediates, general conclusions are hard to be drawn. Proof will be given that, in several cases, the efficiency of the reductive amination of aliphatic aldehydes can be significantly improved by prehydrogenation of the cationic [Rh(dppb)(COD)]+ complex.