We successfully synthesize three different tertiary amine phosphinoamine ligands, which are 1-(2-(dicyclohexylphosphino)phenyl)pyrrole (L2), N-(2-(dicyclohexylphosphino)phenyl) morpholine (L3), and N-(2-(diisopropylphosphino)phenyl)morpholine (L4) separately. With another referenced ligand o-(dicyclohexylphosphino)biphenyl (L1) as comparison and test the reactivities toward palladium and nickel by in situ method with the four different ligands. We test Kumada-Corriu coupling reactivity of different nickel precursors to L1, L2 and L3, surprisingly, we find that under room temperature, reaction of NiCl2(DME) as precursor and TMEDA (1.1 equiv.) as ligand to replace phosphinoamine ligands (L1¡BL2¡BL3) can effectively couple iododecane with hexyllmagnesium bromide, and the catalytic condition possesses quite high selectivity. This new Ni-catalyzed cross-coupling reactions employing secondary isopropylmagnesium chloride have led to the exclusive formation of linear isomerized cross-coupling products due to reinsertion after rapid £]-H elimination.