2-Methylimidazole-1-(N-tert-octyl)sulfonimidoyl fluoride: A Bench-Stable Alternative to SOF4 as Precursor to N,O-Substituted S(VI) Compounds.

S(VI) compounds with multiple N or O substituents are  often difficult to make and several crucial routes, such as multimodal SuFEx (Sulfur (VI) Fluoride Exchange) chemistry, rely on the highly useful but hazardous SOF4 gas. Safety issues and inaccessibility of SOF4 strongly hamper the developments of these organic compounds. Here we describe the synthesis and applications of 2-methylimidazole-1-(N-tert-octyl)sulfonimidoyl fluoride (ImSF), a novel bench-stable analogue of SOF4. ImSF is synthesized on a gram scale via a double fluorination of t-OctNSO. We show ImSF can undergo substitution reactions with phenols and amines, which lead to sulfurimidates and sulfuramidimidates, respectively, the intrinsically chiral analogous of medicinally relevant sulfates and sulfamates in which an S=O moiety is replaced by S=NR unit. Finally we demonstrate that such substitutions can occur enantiospecifically, providing the first entry to chiral sulfurimidates and sulfuramidimidates.

Enantiospecific Synthesis of Aniline-Derived Sulfonimidamides.

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