A stereocontrolled synthesis of 伪-amino-伪鈥?alkoxy ketones is described. This pH-neutral copper(I) thiophene-2-carboxylate (CuTC)-catalyzed cross-coupling of amino acid thiol esters and chiral nonracemic 伪-alkoxyalkylstannanes gives 伪-amino-伪鈥?alkoxy ketones in good to excellent yields with complete retention of configuration at the 伪-amino- and 伪-alkoxy-substituted stereocenters.