Two novel cross-linked polystyrene-supported N-sulfonylated beta-aminoalcohol resins 13 and 14 have been prepared from radical zations of styrene, divinylbenzene, and styrenes bearing a para-substituent of N-sulfonylated aminoalcohol. Resins 13 and 14 were in high yields of 85.8 and 84.7%, and were characterized by IR and solid state C-13 NMR spectroscopies. Elemental analyses reveal that I of resin 13 contains 0.93 mmol bidentate N-sulfonylated beta-aminoalcohol. The ligand content in tridentate resin 14 is calculated to 0.95 mmol/g. The Ti(O-i-Pr)(4)/13 catalytic system works excellently in asymmetric ZnEt2 additions to aldehydes affording secondary in >= 90% ee. Resin 13 can be reused 9 times without losing any activity, giving the product with enantioselectivi ties >= 87% ee. The system was used only once in asymmetric AlEt3 additions to a variety of aldehydes affording secondary alcohols in good to excellent lectivities from 73 to 92% ee. (c) 2008 Elsevier Ltd. All rights reserved.