Group 4 metal complexes based on chiral biaryl ligands are readily prepared by a convenient amine elimination procedure, and they are efficient catalysts for the asymmetric hydroamination/cyclization of aminoalkenes. The biaryl-based ligands are highly modular enabling facile tuning of the catalyst reactivity and selectivity. The corresponding heterocyclic products have been obtained in excellent enantiomeric excesses (up to 93%) using sterically hindered C 2 -symmetric titanium and zirconium mesitoylamidate complexes such as [1,1′-(C 10 H 10 ) 2 -2,2′-{NCO(2,4,6-Me 3 C 6 H 2 )} 2 ]M(NMe 2 ) 2 (M=Ti, Zr). These results are presented in this short review.