2‐Methylimidazole‐1‐(<i>N</i>‐<i>tert</i>‐octyl)sulfonimidoyl Fluoride: A Bench‐Stable Alternative to SOF<sub>4</sub> as Precursor to N,O‐Substituted S(VI) Compounds
Natassa Lional, Fedor M. Miloserdov, Han Zuilhof
Abstract
Abstract 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 SOF 4 gas. Safety issues and inaccessibility of SOF 4 strongly hamper the developments of these organic compounds. Here we describe the synthesis and applications of 2‐methyl im idazole‐1‐( N ‐ tert ‐octyl) s ulfonimidoyl f luoride (ImSF), a novel bench‐stable analogue of SOF 4 . 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.