Novel sulfamide-amine alcohol ligands (6) derived from (-)-ephedrine (4a) and (+)-pseudoephedrine (4b) with multiple stereogenic centers were applied to the catalytic asymmetric addition of diethylzinc to aldehydes, providing (S)-products in high yields and good enantioselectivities. These sulfamide-amine alcohols together with Ti((OPr)-Pr-i)(4) were shown to obtain the (R)-products in significant enantiomeric excesses (e.e.) and high yields. In addition, sulfamide-amine alcohols were superior to the original chiral sources 4a and 4b, which afforded no enantioselectivity in the Ti((OPr)-Pr-i)(4) -mediated reaction. (C) 2004 Elsevier B.V. All rights reserved.