Enantiospecific Synthesis of Aniline-Derived Sulfonimidamides.

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.