17530-97-1

Upstream product

• 134948-24-6 S-methyl α-(trimethylsilyl)ethanimidothioate 
• 7031-27-8 (phenylthio)acetic acid chloride 
• 62-53-3 aniline 
• 4686-01-5 N-phenyl-2-benzenesulfanylacetamide 
• 4972-29-6 benzenesulphinyl chloride 
• 134916-85-1 N-phenyl-(trimethylsilyl)ketenimine 

Relevant academic research and scientific papers

Studies on the oxidation and fluorination of α-phenylsulfanylacetamides using difluoroiodotoluene

α-Phenylsulfanylacetamides are fluorinated in the α-position when treated with difluoroiodotoluene (DFIT) in a fluoro-Pummerer reaction. For N- phenyl amides an intramolecular Friedel-Crafts reaction may compete and produce heterocycles. (C) 2000 Elsevier Science Ltd.

Fluorination of sulfanyl amides using difluoroiodoarene reagents

A range of sulfur-containing amides have been fluorinated with the hypervalent iodine difluoride reagents 1, and two principal reaction pathways identified. Cephalosporin esters 2 having a heteroatom in the α-position to sulfur undergo fluorination in DCM with cleavage of the carbon-sulfur bond to form novel fluorinated β-lactams 4. Sulfides with electron-withdrawing groups in the α-position undergo α-fluorination in a process analogous to the classical Pummerer reaction. This Fluoro-Pummerer reaction has been exemplified for a range of simple α-phenylsulfanylacetamides 14-19. When β-hydrogens are present in the substrate a different route is followed, with deprotonation by basic fluoride taking place to yield vinyl sulfides 41-43. When an excess of the fluorinating reagent is used these vinyl sulfides can undergo further reaction in a novel tandem Pummerer-Additive-Pummerer process to yield α,β-difluoro sulfides 45-47.

Reactivity of N-phenyl silylated ketenimines with electrophilic reagents

We report the reactivity of new Cβ silylated ketenimines (4, 5, 6) and lithiated-silylated ketenimine 3 [easily generated from lithiated S-methyl- N-phenyl-trimethylsilylethanimidothioate 2] toward electrophilic reagents. Reactions of these ketenimines with strong electrophilic reagents such as sulfanyl chloride (PhSCl) gave access to new sulfanylated ketenimines. With less reactive species [benzenesulfinyl chloride (PhS(O)Cl), p-toluenesulfonyl chloride, trimethylhalosilanes, diisopropyl chlorophosphate, acetyl chloride and propylene oxide] and 3, the addition took place either on Cβ or on the nitrogen atom leading to relatively unstable functionalised ketenimines or new silylated ynamines respectively.