A library of 5,5'-disubstituted BINAP derivatives were synthesized in good yield from optically pure BINAP and evaluated for the Rh-catalyzed homogeneous asymmetric hydrogenation of (alpha)-acylaminoacrylate ester, with ee of up to 77% being obtained with the phenyl derivative. The enantiomeric excess variation was followed according to the groups introduced in the 5,5'-position of BINAP and for a range of pressure from 5 to 30 bar. (c) 2007 Published by Elsevier B.V.