The stereoselective synthesis of alpha,alpha-difluoro-beta-hydroxyketones of high enantiomeric purity is described starting from optically active alpha,alpha-difluoro-beta-hydroxy esters. The esters were converted to the corresponding N-methoxy-N-methyl amides, which were treated with Grignard and organolithium reagents to provide the alpha,alpha-difluoro-beta-hydroxyketones with up to 100% ee. (C) 1999 Elsevier Science S.A. All rights reserved.