94404-29-2

Upstream product

• 1879-16-9 1-methoxy-4-methylsulfanyl-benzene 
• 696-63-9 4-Methoxybenzenethiol 
• 373-53-5 fluoroiodomethane 
• 3517-99-5 1-methoxy-4-(methylsulfinyl)benzene 
• 593-53-3 Methyl fluoride 

Downstream Products

• 94404-22-5 Fluoromethyl 4-methoxyphenyl sulfoxide 
• 81931-98-8 1-<(Difluoromethyl)thio>-4-methoxybenzene 

Relevant academic research and scientific papers

Nickel-Catalyzed Decarbonylative Synthesis of Fluoroalkyl Thioethers

This report describes the development of a nickel-catalyzed decarbonylative reaction for the synthesis of fluoroalkyl thioethers (RFSR) from the corresponding thioesters. Readily available, inexpensive, and stable fluoroalkyl carboxylic acids (RFCO2H) serve as the fluoroalkyl (RF) source in this transformation. Stoichiometric organometallic studies reveal that RF-S bond-forming reductive elimination is a challenging step in the catalytic cycle. This led to the identification of diphenylphosphinoferrocene as the optimal ligand for this transformation. Ultimately, this method was applied to the construction of diverse fluoroalkyl thioethers (RFSR), with R = both aryl and alkyl.

Direct and Chemoselective Electrophilic Monofluoromethylation of Heteroatoms (O-, S-, N-, P-, Se-) with Fluoroiodomethane

The commercially available fluoroiodomethane represents a valuable and effective electrophilic source for transferring the CH2F unit to a series of heteroatom-centered nucleophiles under mild basic conditions. The excellent manipulability offered by its liquid physical state (bp 53.4 °C) enables practical and straightforward one-step nucleophilic substitutions to retain the chiral information embodied, thus allowing it to overcome de facto the requirement for fluoromethylating agents with no immediate access. The high-yielding methodology was successfully applied to a variety of nucleophiles including a series of drugs currently in the market.

Bis(2-methoxyethyl)aminosulfur trifluoride: A new broad-spectrum deoxofluorinating agent with enhanced thermal stability

Bis(2-methoxyethyl)aminosulfur trifluoride, (CH3OCH2CH2)2NSF3 (Deoxo-Fluor reagent), is a new deoxofluorinating agent that is much more thermally stable than DAST (C2H5)2NSF3 and its congeners. It is effective for the conversion of alcohols to alkyl fluorides, aldehydes/ketones to the corresponding gem-difluorides, and carboxylic acids to the trifluoromethyl derivatives with, in some cases, superior performance compared to DAST. The enhanced stability is rationalized on the basis of conformational rigidity imposed by a coordination of the alkoxy groups with the electron-deficient sulfur atom of the trifluoride.

Facile synthesis of α-fluoroalkyl sulfides under the oxidative desulfurization-fluorination conditions

Upon treatment with n-Bu4NH2F3 and 1,3-dibromo-5,5- dimethylhydantoin, various organic sulfides underwent a Pummerer-type rearrangement, followed by fluorination, to give α-fluoro sulfides. The fluoro-Pummerer rearrangement, when applied to RCH(SMe)CF2SMe, gave trifluoro sulfides RCF(SMe)CF2SMe. When an HF-pyridine reagent was used as the fluorinating agent, an oxidative desulfurization-fluorination reaction occurred depending on the structure of the substrates.

Fluoro-Pummerer rearrangement under oxidative desulfurization fluorination conditions. Facile synthesis of oligofluoroalkyl sulfides

Upon treatment with n-Bu4NH2F3 and 1,3-dibromo-5,5-dimethylhydantoin, various organic sulfides were readily fluorinated to give α-fluoro sulfides. When (HF)9-Py was used as the fluorinating agent, normal oxidative desulfurization fluorination occurred depending on the structure of the substrates.

Efficient Conversions of Thioethers to α-Fluoro Thioethers with DAST or DAST/Antimony(III) Chloride

Dialkyl or alkyl aryl thioethers, including nucleoside thioethers, undergo virtually quantitative conversion to α-fluoro thioethers with (diethylamino)sulfur trifluoride (DAST) in dichloromethane at ambient temperature.Antimony(III) chloride catalyzes the process.