2-Methylimidazole-1-(N-tert-octyl)sulfonimidoyl Fluoride: A Bench-Stable Alternative to SOF 4 as Precursor to N,O-Substituted S(VI) Compounds

• Published in: Angewandte Chemie International Edition Vol. 63; no. 36; p. e202406915
• Main Authors: Lional, Natassa, Miloserdov, Fedor M, Zuilhof, Han
• Format: Journal Article
• Language: English
• Published: Germany 02-09-2024
• Subjects: SuFEx; Sulfur (VI); sulfuramidimidates; sulfurimidates; SOF4
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202406915

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
gas. Safety issues and inaccessibility of SOF
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 SOF
. 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.