Enantiospecific Synthesis of Aniline-Derived Sulfonimidamides

A mechanochemical synthesis of sulfonimidamides by iron(II)‐catalyzed exogenous ligand‐free N‐acyl nitrene transfer to sulfinamides is reported. The one‐step method tolerates a wide range of sulfinamides with various substituents under solvent‐free ambient conditions. Compared to its solution‐phase counterpart, this mechanochemical approach shows better conversion and chemoselectivity. Mechanistic investigations by ESI‐MS revealed the generation of crucial nitrene iron intermediates.

Mechanochemical Iron‐Catalyzed Nitrene Transfer Reactions: Direct Synthesis of N‐Acyl Sulfonimidamides from Sulfinamides and Dioxazolones

Pan,

Mulks,

et al. 2023

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

Lional,

Miloserdov,

Zuilhof

2024

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.

The Modular Synthesis of Sulfondiimidoyl Fluorides and their Application to Sulfondiimidamide and Sulfondiimine Synthesis

Ding,

Bell,

Willis

2024

A modular synthesis of sulfondiimidoyl fluorides ‐ the double aza‐analogues of sulfonyl fluorides ‐ allowing variation of the carbon and both nitrogen‐substituents is reported. The chemistry uses readily available organometallic reagents, commercial sulfinylamines, simple electrophiles, and N‐fluorobenzenesulfonimide (NFSI), as the starting materials. The reactions are broad in scope, efficient, and scalable. We show that the sulfondiimidoyl fluoride products can be combined with amines to provide sulfondiimidamides, and with organolithium reagents to provide sulfondiimines, and that reactivity in these transformations can be modulated by variation of the N‐substituents.