Phosphines versus phosphinites as ligands in the rhodium catalyzed asymmetric hydrogenation of imines: a systematic study

Abstract

The asymmetric hydrogenation of N-(1-phenylethylidene)benzylamine with a range of rhodium(I)-diphosphine and diphosphinite catalysts is studied. The reaction is strongly sensitive to the size of the metal chelate. Complexes based on five- and six-membered chelates or electron-rich alkylphosphines gave poor or moderate conversions. The reactivity of diphosphine catalysts could be increased by the addition of p-toluenesulfonic acid. Unexpectedly, Rh-complexes based on chiral diphosphinites and a diphosphite also rapidly converted the substrate to the desired amine. Highest efficiency was observed with a rhodium(I) complex with ( R, R)-1,2-cyclohexanol-bisdiphenylphosphinite [( R, R)-bdpch] as chiral ligand. Without any additive complete hydrogenation of the imine was achieved within 5 h. The product was produced in an enantioselectivity of 71%.