An efficient method for the catalytic asymmetric additions to aldehydes using organolithium reagents and titanium(IV) isopropoxide in the presence of commercially available and relatively inexpensive diol ligands, such as (S)-BINOL or d-TADDOL has been developed. Good to excellent yields (up to 92%) and enantioselectivities (up to 94%) of the corresponding secondary alcohol products can be obtained following a simple procedure at relatively mild reaction temperatures.(R)-1-Phenylpentan-1-olC11H16O[α]D25.3 = +32.3 (c 2.0, CHCl3), 92% eeSource of chirality: Asymmetric synthesisAbsolute configuration: (R)(R)-1-p-Tolylpentan-1-olC12H18O[α]D29.4 = +15.9 (c 1.0, C6H6), 92% eeSource of chirality: Asymmetric synthesisAbsolute configuration: (R)(R)-1-(4-(Trifluoromethyl)phenyl)pentan-1-olC12H15F3O[α]D31.7 = +8.1 (c 1.0, CHCl3), 93% eeSource of chirality: Asymmetric synthesisAbsolute configuration: (R)(R)-1-(4-Fluorophenyl)pentan-1-olC11H15FO[α]D29.2 = +11.5 (c 1.0, CHCl3), 88% eeSource of chirality: Asymmetric synthesisAbsolute configuration: (R)(R)-1-(4-Chlorophenyl)pentan-1-olC11H15ClO[α]D28.5 = +17.4 (c 1.0, C6H6), 94% eeSource of chirality: Asymmetric synthesisAbsolute configuration: (R)(R)-1-(Naphthalen-2-yl)pentan-1-olC15H18O[α]D29.7 = +13.4 (c 1.0, CHCl3), 86% eeSource of chirality: Asymmetric synthesisAbsolute configuration: (R)(R)-1-(Thiophen-2-yl)pentan-1-olC9H14OS[α]D30.5 = +12.2 (c 1.0, CHCl3), 63% eeSource of chirality: Asymmetric synthesisAbsolute configuration: (R)(R,E)-1-Phenylhept-1-en-3-olC13H18O[α]D29.8 = −1.0 (c 1.0, CHCl3), 67% eeSource of chirality: Asymmetric synthesisAbsolute configuration: (R)(R)-1-Cyclohexylpentan-1-olC11H22O[α]D24.1 = +6.3 (c 2.0, CHCl3), 68% eeSource of chirality: Asymmetric synthesisAbsolute configuration: (R)(R)-1-PhenylethanolC8H10O[α]D25.6 = +42.1 (c 1.0, CHCl3), 82% eeSource of chirality: Asymmetric synthesisAbsolute configuration: (R)(R)-1-(4-Fluorophenyl)ethanolC8H9OF[α]D30.4 = +18.3 (c 1.0, CHCl3), 84% eeSource of chirality: Asymmetric synthesisAbsolute configuration: (R)(R)-1-p-TolylethanolC9H12O[α]D26.2 = +35.0 (c 1.0, CHCl3), 81% eeSource of chirality: Asymmetric synthesisAbsolute configuration: (R)(R)-1-Phenylheptan-1-olC13H20O[α]D30.2 = +25.0 (c 1.0, CHCl3)Source of chirality: Asymmetric synthesisAbsolute configuration: (R)(R)-(4-(Trifluoromethyl)phenyl)phenylmethanolC14H11F3O[α]D30.5 = −25.0 (c 1.0, CHCl3)Source of chirality: Asymmetric synthesisAbsolute configuration: (R)

The asymmetric addition reactions between varied nonaromatic aldehydes and diethylzinc catalyzed by chiral phosphoramide L1 and thiophosphorodiamide L4 were thoroughly investigated. Both ligands worked very well for α-branched aliphatic and α-branched α,β-unsaturated aldehydes. For α-nonbranched aliphatic aldehydes, L4 behaved much better than L1. For α-nonbranched α,β-unsaturated aldehydes, L4 showed high enantioselectivities and L1 only gave racemic alcohol products.