The new amidophosphine-phosphinite (AMPP) ligands 4a– g (called tLANOP ligands) derived from the chiral hydroxy amide ( R)- or ( S)-2-hydroxy-3,3, N-trimethylbutyramide have been prepared in 48–83% yield. The crystal structures of the square planar complexes [( SP-4-3)-Pd(( R)-dmphea)(( S)- 4a)]BF 4 and [Rh(( R)- 4a)(COD)]BF 4 have allowed the absolute configurations of the ligands to be assigned. In both complexes the 7-membered chelating ring of 4a has virtually the same twist-boat conformation. With this class of ligands the rhodium catalyzed asymmetric hydrogenation of 4-oxoisophorone enol acetate gave ( S)-phorenol acetate in up to 71% ee. The iridium catalyzed asymmetric hydrogenation of the cyclic iminium salts 16a and 16b afforded after work-up the corresponding cyclic secondary amine ( S)- 17 in up to 86% ee, when bulky groups were present on the phenyl substituents on the two phosphorus atoms.