Aspects of the chemistry of sulfimides (sulfilimines) which are of importance in stereoselective synthesis are reviewed. The three principal sections cover bonding and configuration, preparation of enantiomerically enriched sulfimides from chiral and achiral starting materials and applications of chiral sulfimides in stereoselective synthesis, including stereospecific conversion to other chiral sulfur compounds, stereospecific electrocyclic reactions, diastereoselective and enantioselective reactions. Parallels are drawn with related reactions of other chiral sulfur compounds.