Enantiospecific Synthesis of Aniline-Derived Sulfonimidamides

Reaction of sulfonimidoyl fluorides with anilines and Ca(NTf2)2results 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(NTf2)2and the formation of a SN2-like transition state, in which leaving F–coordinates with the Ca2+ion.