In this work cyclic secondary amines were the preferred substrates in our initial trials (Table ). When utilizing dimethyl substituted cyclic diaryliodonium 9a and 1,2,3,4-tetrahydroquinoline 10a as the model substrates, CaO was found to be the optimal base, effectively minimizing the formation of protonated and hydroxylated byproducts. The reaction catalyzed by Cu(OTf)2/L1 in CH2Cl2 yielded 57% of 11a with 89% ee (entry 1). The corresponding p-methoxyphenylacetylenyl substituted ligand L3 substantially decreased both reactivity and selectivity (entry 2). In contrast to L3, the phenylacetylene phenyl-substituted ligand L4 exhibited an excellent enantioselectivity with a moderate yield (entry 3). The ligand L5, featuring 3,5-dimethylphenyl arms, produced moderate yield and stereoselectivity (entry 4). With the 2-(9',9'-dimethyl-9H-fluorenyl) substituents (L6), a large increase in enantioselectivity (95%) was observed with concomitant an increase in yield (89%) (entry 5), however, the corresponding isomer (L7) exhibited a decent stereo-induction ability (entry 6). Replacing the 9',9'-dimethyl-9'H-fluorenyl with heterocyclic 2-dibenzo[b,d]furanyl (L8) or 2-(9'-phenyl-9'H-carbazolyl) (L9) group did not improve the stereoselectivity (entries 7 and 8). Further investigation revealed that CuSCN showed better performance than Cu(OTf)2, resulting a yield of 11a while maintaining the high stereoselectivity (entries 9 and 10). With ,'-dimethyl at the pyridine rings, the more sterically hindered L2 resulted in poor reactivity, and concomitant a decreased stereoinduction (entry 11). Reaction scope and selectivity: Upon establishing the optimal conditions, we proceeded to explore the substrate scope of this reaction as detailed in Figure . A variety of substituted tetrahydroquinoline were employed as the nucleophilic coupling components, encompassing 6-alkyl, 6-halide, 7-halide, 4,4-dimethyl groups (11b-11g). The cyclic secondary amines with a accessory, i.e. 3,4-dihydro-2H-benzo[b] [1,4]oxazine (11h) or 3,4-dihydro-2Hbenzo[b] [1,4]thiazine (11i), exhibited exceptional stereoselectivity. The seven-membered cyclic amine, 2,3,4,5-tetrahydro-1H-benzo[b]azepine (11j), maintained the enantioselectivity observed as 11a, though the yield of the ring-opened product decreased noticeably. The absolute configuration of (R)-11j was confirmed by the single crystal X-ray diffractional study (CCDC 2326407). Indoline also facilely coupled with 9a to afford 11k in a high ee value (88%). This asymmetric ring-opening reaction was also applicable to acyclic secondary aniline derivatives. The electronic perturbations at the aromatic ring of acyclic secondary anilines include alkyl, phenyl, as well as an extended aromatic system, naphthyl or benzofurans (11l-11o, and 11q-11u). It was observed that strong electron-withdrawing group, i.e. NO2, would fully inhibit its reactivity (11p). Unfortunately, the dialkyl amines currently did not fall within the scope of this method, resulting in low stereoselectivity. The ortho,ortho'-dibrominated cyclic diaryiodonium salt worked smoothly to deliver 11v in excellent yield and enantioselectivity, whereas the dichloro analogue afforded a modest 46% yield with a considerable decrease in enantiomeric excess (11w). The axially chiral aniline derivatives with binaphthyl backbone or tetramethyl substituted biphenyls were also successfully synthesized, achieving excellent enantioselectivity (11x-11z). The robust of the reaction was demonstrated by a smooth reaction when it was conducted under 1.0 mmol scale (11a). were obtained under the catalysis of CuSCN/L6 system, while dramatic drop of yields of all the three products was observed when L10 was employed (Figure ). The non-fused bipyridine L11 also displayed poor reactivity in this catalytic ring-opening reaction. The aromatic 1,10-phenanthroline L12 exhibited promising reactivity when 1,2,3,4tetrahydroquinoline was employed as the substrate, however, 11h and 11o were still formed in low yields. These control experiments have underscored that the binaphthyl skeleton not only creates a chiral environment, but also exerts an influence on the reactivity of the corresponding metal complex.