Mechanochemical Enantiospecific Syntheses of Sulfonimidate Esters and Sulfonimidamides by Various S(VI) Exchange Reactions

Mechanochemical S(VI) exchange reactions are developed on chiral S(VI)–F and S(VI)–Cl centers that are fast, solvent–free, high–yielding, and enantiospecific. This approach is used to synthesize a range of sulfonimidate esters and sulfonimidamides from sulfonimidoyl fluorides and chlorides under mild reaction conditions. The broad scope of this method is demonstrated by its successful reactivity with a range of phenols and both primary and secondary anilines. Furthermore, substitution in 4–nitrophenol-derived S(VI) species with substituted phenols (SuPhenEx) is successfully achieved. This approach is faster, greener, and reduces the need for the formation of fluorinated species, while retaining many of the advantages of SuFEx and related S(VI) substitution reactions.