Properly protected glycinates (Schiff base, alkyl/aryl ester) cleanly reacted with chiral sulfinyl‐derived difluoro(phosphoryl)aldimines under ambient conditions in THF in the presence of a catalytic amount of Cs2CO3. The procedure was operationally simple and provided the target addition products in good (60–80 %) yields with excellent (99:1) diastereoselectivity. This approach allowed the preparation of a structural type of biologically interesting molecules comprising α,β‐diamino acid, carboxylic acid, and phosphonic acid structural features. Chemoselective operation of the α‐ and β‐amino functional groups was demonstrated by the preparation of all‐α‐ and mixed‐α,β‐amino acid derived dipeptides.