The catalytic enantioselective hydroarylation of 1,1-disubstituted alkenes proceeded by using a cationic iridium/(R)-binap complex to give the corresponding adducts in high yields with high enantioselectivity. The reaction of arenes substituted with heteroaromatic directing groups proceeded to give the addition products linear-selectively. Methallylamine derivatives were good acceptors to obtain high enantioselectivities. The adduct bearing maleimide moiety was readily transformed into the β-chiral amine derivative without loss of the enantiomeric purity.