Sulfonimidamides by Sequential Mechanochemical Chlorinations and Aminations of Sulfinamides

Abstract

Here, we report the first mechanochemical synthesis of sulfonimidamides. The one-pot, two-step method requires neither a solvent nor inert conditions. In a mixer mill, sulfinamides are rapidly converted to sulfonimidoyl chlorides by oxidative chlorination with N-chlorosuccinimide (NCS). Subsequent substitutions with amines provides a wide range of diversely substituted sulfonimidamides.

Ball milling synthesis of S-quinolyl xanthates via coupling of haloquinolines with potassium O-alkyl xanthates

“…8 In contrast to solvent-based reaction systems, most of the ball-milling reactions are performed under solvent-free conditions thereby achieving increased sustainability. In recent years, various ball milling promoted organic transformations mainly including metal catalyzed/mediated coupling reactions, nucleophilic substitution reactions, condensation reactions, redox reactions and cycloaddition reactions have been widely reported by Bolm, 9 Friščić, 10 and others. 11 In many cases, ball milling reactions have shown more advantages over traditional solvent-based organic reactions with regard to shorter reaction times and higher yields.…”

One-Pot Tandem Oxidative Bromination and Amination of Sulfenamide for the Synthesis of Sulfinamidines

“…First, sulfinamidine 4 could be smoothly converted to the corresponding alkylated derivatives 54 and 55 in high yields. Next, the sulfinamidine product could be easily converted to the corresponding sulfonimidamide with high efficiency . For example, treatment of the sulfinamidines 4 with PhI­(OAc) 2 in DCE allowed for the formation of 56 in 81% yield.…”

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

“…Dioxazolones, which are well‐established, stable acyl nitrene precursors with numerous applications in related sulfur imidations [15] and C−H‐bond amidations, [16] were identified as attractive reagents. In addition, we set the goal to search for a simple and non‐precious metal catalyst to be applied under mechanochemical conditions, which we envisaged to have two additional advantages over existing technologies: First, being able to avoid a solvent and, second, reaching a higher efficiency with improved sustainability [17–19] . As a results of this endeavor, we now report an iron‐catalyzed mechanochemical approach to sulfonimidamides from sulfinamides and dioxazolones under ambient conditions in air (Scheme 1B, bottom).…”