A new series of chiral bis-ligated group 4 complexes have been prepared from the reaction between M(NMe 2 ) 4 (M=Ti, Zr) and C 1 -symmetric biaryl-based NO 2 ligands, (R)-2-(mesitoylamino)-2′-methoxy-1,1′-binaphthyl (1H), (R)-2-(mesitoylamino)-2′-methoxy-6,6′-dimethyl-1,1′-biphenyl (2H), (S)-5,5′,6,6′,7,7′,8,8′-octahydro-2-(mesitoylamino)-2′-methoxy-1,1′-binaphthyl (3H), (R)-2-(3,5-di-tert-butyl-2-hydroxyphenylmethyleneamino)-2′-methoxy-1,1′-binaphthyl (4H), (R)-2-(3-tert-butyl-2-hydroxyphenylmethyleneamino)-2′-methoxy-6,6′-dimethyl-1,1′-biphenyl (5H), which are derived from (R)-2-amino-2′-methoxy-1,1′-binaphthyl, (R)-2-amino-2′-methoxy-6,6′-dimethyl-1,1′-biphenyl or (S)-5,5′,6,6′,7,7′,8,8′-octahydro-2-amino-2′-methoxy-1,1′-binaphthyl. Treatment of M(NMe 2 ) 4 with 2 equiv. of mesitoylamides 1H, 2H or 3H gives, after recrystallization from a toluene or n-hexane solution, the bis-ligated chiral titanium amides (1) 2 Ti(NMe 2 ) 2 (6), (2) 2 Ti(NMe 2 ) 2 (8), (3) 2 Ti(NMe 2 ) 2 (10), and zirconium amides (1) 2 Zr(NMe 2 ) 2 (7), (2) 2 Zr(NMe 2 ) 2 (9), (3) 2 Zr(NMe 2 ) 2 (11), respectively, in good yields. Under similar reaction conditions, treatment of M(NMe 2 ) 4 with 2 equiv. of Schiff base ligands 4H or 5H gives, after recrystallization from a toluene solution, the chiral bis-ligated titanium complex {(R)-2-[3,5-(Me 3 C) 2 -2-O-C 6 H 2 CH(NMe 2 )N]-2′-(MeO)-1,1′-C 20 H 12 } 2 Ti (12) and zirconium complex {(R)-2-[3-Me 3 C-2-O-C 6 H 3 CH(NMe 2 )N]-2′-(MeO)-1,1′-(6-Me-C 6 H 3 ) 2 }(5)ZrNMe 2 (13), respectively, in good yields. All new compounds have been characterized by various spectroscopic techniques, and elemental analyses. The solid-state structures of compounds 1H, 6, 8, 9, 12 and 13 have further been confirmed by X-ray diffraction analyses. The titanium and zirconium amides are active catalysts for the asymmetric hydroamination/cyclization of aminoalkenes, affording cyclic amines in moderate to excellent yields with good ee values.