Abstract A series of new chiral phosphine-aminophosphine ligands [(R)-HW-Phos] has been prepared from (R)-1, 2, 3, 4-tetrahydro-1-naphthylamine through a two-step procedure, and successfully applied in the rhodium-catalyzed asymmetric hydrogenation of various functionalized olefins such as α-enol ester phosphonates, α-enamido phosphonates,(Z)-β- (acylamino) acrylates and so on. Excellent enantioselectivities have been achieved in the ...