Chiral 3,3'-bis(trisarylsilyl)-substituted binaphtholate rare earth metal complexes (R)-[Ln-{Binol-SiAr3}(o-C6H4CH2NMe2)(Me2NCH2Ph] (Ln = Sc, Lu, Y; Binol-SiAr3 = 3,3'-bis(trisarylsilyl)-2,2'-dihydroxy-1,1'-binaphthyl; Ar = Ph (2-Ln), 3,5-xylyl (3-Ln)) and (R)-[La{Binol-Si(3,5-xylyl)(3)}{E(SiMe3)(2)}(THF)(2)] (E = CH(4a), N(4b)) are accessible via facile arene, alkane, and amine elimination. They are efficient catalysts for the asymmetric hydroamination/cyclization of aminoalkenes, giving TOF of up to 840 h(-1) at 25 degrees C for 2,2-diphenyl-pent-4-enylamine (5c) using (R)-2-Y. Enantioselectivities of up to 95% ee were achieved in the cyclization of 5c with (R)-2-Sc. The reactions show apparently zero-order rate dependence on substrate concentration and first-order rate dependence on catalyst concentration, but rates depend on total amine concentrations. Activation parameters for the cyclization of pent-4-enylamine using (R)-2-Y (Delta H(S)* = 57.4-(0.8) kJ mol(-1) and Delta S(S)(double dagger) = -102(3) J K-1 mol(-1); Delta H(R)(double dagger) = 61.5(0.7) kJ mol(-1) and Delta S(R)(double dagger) = -103(3) J K-1 mol-1) indicate a highly organized transition state. The binaphtholate catalysts were also applied to the kinetic resolution of chiral alpha-substituted aminoalkenes with resolution factors f of up to 19. The 2,5-disubstituted aminopentenes were formed in 7:1 to >= 50:1 trans diastereoselectivity, depending on the size of the alpha-substituent of the aminoalkene. Rate studies with (S)-1-phenyl-pent-4-enylamine ((S)-15e) gave the activation parameters for the matching (Delta H-double dagger = 52.2(2.8) kJ mol(-1), Delta S-double dagger = -127(8) J K-1 mol(-1) using (S)-2-Y) and mismatching (Delta H-double dagger = 57.7(1.3) kJ mol(-1), Delta S-double dagger = -126(4) J K-1 mol(-1) using (R)-2-Y) substrate/catalyst combination. The absolute configuration of the Mosher amide of (2S)-2-methyl-4,4-diphenyl-pyrrolidine and (2R)-methyl-(5S)-phenyl-pyrrolidinium chloride, prepared from (S)-15e, were determined by crystallographic analysis. Catalyst (R)-4a showed activity in the anti-Markovnikov addition of n-propylamine to styrene.