An efficient method has been developed for the enantioselective synthesis of fully protected α-quaternary α-hydroxy-β-amino esters via the coupling of three components: aryl Grignard reagents (or methyllithium), silyl glyoxylate, and N-tert-butanesulfinyl imines. This protocol enables successive formation of two C-C bonds and two adjacent chiral carbons with high stereocontrol in a one-pot operation.