Chiral titaniumcomplex (1), prepared in situ from optically pure binaphthol and diisopropoxytitanium dihalide in the presence of molecular sieves, is shown to catalyze the additionreactions of crotylsilanes and -stannanes to glyoxylates to afford (syn)-α-hydroxy-β-methyl esters in highly scalemic forms with high diastereoselectivity.