Next, we investigated derivatization of our newly developed axially chiral biphenyldiol cores. It is well known that the phosphoramidites of axially chiral biaryldiols are the privileged ligands in the asymmetric synthesis . At first, we prepared the BIPHNOL-derived phosphoramidite ligands according to previous procedures . As shown in Fig. , reaction of chiral secondary amine 26 with PCl3 in dry toluene provided 27, and treatment of 27 with our axially chiral biphenyldiols ((S)-L1, L2 or L3) gave the corresponding phosphoramidite ligands (S)-L14, L15 or L16 in 90%, 83% and 71% yields, respectively, for the two step reactions. Subsequently, we prepared chiral phosphoramidite ligand (S)-L18 in 56% yield via the similar procedures. To evaluate reactivity and enantioselectivity of our newly developed chiral phosphoramidite ligands in asymmetric catalysis, two reactions were selected as the examples. Yang and Zhao reported the Pd-catalyzed [4+2] cycloaddition of benzofuran-derived azadienes with vinyl benzoxazinanones, and they found that cycloaddition of 30 with 31 in the presence of phosphoramidite ligand L12 provided high yield (92%) and ee value (92% ee). However, the reaction was incomplete when (S)-L13 was used as the ligand (Fig. ) . We attempted the cycloaddition of 30 with 31 in the presence of our chiral phosphoramidite ligands (S)-L14, L15 or L16. Inspiringly, (S)-L16 provided excellent diastereo-and enantioselectivity (>20:1 dr, 97% ee) (Fig. ). Subsequently, another example was surveyed. In 2014, Lu and Xiao developed the Pd-catalyzed asymmetric decarboxylation-cycloaddition of vinyl benzoxazinanones with sulphur ylides . We investigated efficiency of the previous (S)-L17 and our newly developed (S)-L18 by using asymmetric decarboxylation-cycloaddition of 31 and 33, and the results showed that (S)-L18 was better than (S)-L17 in asymmetric reaction of 31 and 33b (Fig. ).