New phosphine ligands possessing both axial chirality and a chirogenic phosphorus center were prepared from (R)-2-bromo-2'-N,N- (dimethylamino)-1,1'-binaphthyl (1) via a simple Li-halogen exchange protocol. The asymmetric vinylation of a ketone enolate with (RRp)-2-(tert-butylphenylphosphino)-2'- N,N-(dimethylamino)-1,1'-binaphthyl (2a) afforded the coupling product with good enantiomeric excess.