Direct addition of a chiral N-azidoacetyl thiazolidinethione to a variety of dialkyl acetals catalyzed by a commercially available and structurally simple nickel(II) complex gives access in good yields and a highly stereocontrolled manner to anti-beta-alkoxy-alpha-azido carboxylic derivatives which, in turn, can be easily converted into a wide array of enantiomerically pure compounds.