A study of the preparation and of the reactivity of N‐tert‐butanesulfinyl glycosylamines is reported for the first time. As they react readily as latent imine equivalents with a variety of carbon nucleophiles, these new carbohydrate derivatives constitute very useful precursors for the diastereoselective synthesis of bioactive compounds such as iminosugar‐C‐glycosides.

An efficient methodology for the stereoselective and tunable addition of LiCFP(O)(OEt) and BrMgCFP(O)(OEt) reagents to N-t-butanesulfinyl glycosylamines is described with details on the stereochemical effects at play in this process. It provides a practical route to various 1-C-diethylphosphono(difluoromethyl) iminosugars as glycosyl phosphate and sugar nucleotide mimics.