AbstractNew chiral ligands, (S,R,S)‐1, (S,S,S)‐1, (S,S,R)‐1, (S,R,R)‐1, (R,R,R)‐1, (R,R,S)‐1, (R,S,S)‐1, (R,S,R)‐1, (S,R,S)‐2, (S,S)‐3 and (R,S)‐4 with diverse stereogenic centers arising from various diastereomeric combinations of aminoalcohol functionality with (R)‐ and (S)‐1,1‐binaphthol, were prepared and characterized. Catalytically active Ti complexes were generated in situ in the presence of water for the enantioselective ring‐opening reaction of meso‐stilbene oxide, cyclohexene oxide, cyclopentene oxide, and cis‐butene oxide with different anilines as nucleophile. Significantly, catalysts Ti‐(S,R,S)‐1 and Ti‐(R,S,S)‐1 (15 mol %) produced syn‐beta‐amino alcohols of meso‐stilbene oxide with (1S,2S) and (1R,2R) configuration respectively in excellent yields (>98 %) and enantioselectivities (ee value >99 %) in 10 h at room temperature. However, aliphatic/cyclic epoxides with aniline gave better performance with the catalyst Ti‐(S,R,R)‐1. The complex Ti‐(S,R,S)‐1 was successfully subjected to catalyst recovery and recyclability experiments over 6 cycles in the asymmetric ring‐opening of meso‐stilbene oxide with aniline with retention of performance.