Enantiospecific Synthesis of Aniline-Derived Sulfonimidamides

[Image: see text] Reaction of sulfonimidoyl fluorides with anilines and Ca(NTf(2))(2) results in the formation of chiral sulfonimidamides. The reaction proceeds with inversion of the stereocenter at a sulfur atom. Enantiospecificity of the reaction was observed for all studied non-heterocyclic anilines. Combined experimental and computational mechanistic studies highlight chelate-type coordination of the sulfonimidoyl group to Ca(NTf(2))(2) and the formation of a S(N)2-like transition state, in which leaving F(–) coordinates with the Ca(2+) ion.