24021-11-2

Upstream product

• 36141-66-9 ethyl 2-hydroxy-2-(4-methoxyphenyl)acetate 
• 14062-18-1 ethyl p-methoxyphenylacetate 
• 401-55-8 ethyl bromofluoroacetate 
• 5720-07-0 4-methoxyphenylboronic acid 
• 21130-91-6 triethoxy(4-methoxyphenyl)silane 
• 7294-51-1 2,4,6-tris(4-methoxyphenyl)boroxine 
• 100701-49-3 3-ethoxy-2-fluoro-3-oxopropionic acid 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 401-56-9 ethyl chlorofluoroacetate 
• 64-17-5 ethanol 
• 123902-08-9 2-(4-methoxyphenyl)-1-(pyrrolidin-1-yl)ethan-1-one 

Downstream Products

• 112545-98-9 2,2-difluoro-2-(4-methoxyphenyl)acetic acid ethyl ester 

Relevant academic research and scientific papers

Nickel-Catalyzed Cross-Coupling of Ethyl Chlorofluoroacetate with Aryl Bromides

A combinatorial nickel-catalyzed monofluoroalkylation of aryl bromides with the industrial raw regent ethyl chlorofluoroacetate has been developed. The two key factors to successful conversion are the combination of nickel with readily available nitrogen and phosphine ligands and the using of a mixture of different solvents. Mechanistic investigations indicated a new zinc regent might generated in situ and be involved in the reaction process.

Divergent Synthesis of α-Fluorinated Carbonyl and Carboxyl Derivatives by Double Electrophilic Activation of Amides

A straightforward and divergent entry to α-fluorinated carbonyl and carboxyl derivatives is reported. Upon activation of amides with triflic anhydride and a 2-halo-pyridine and subsequent trapping of the resulting keteniminium ions with nucleophiles followed by a second electrophilic activation with NFSI and final hydrolysis, a range of amides can be transformed to α-fluorinated ketones, esters, and amides under mild conditions. Moreover, this reaction can be performed to yield enantioenriched products with a traceless chiral auxiliary.

Copper-Mediated Synthesis of Monofluoro Aryl Acetates via Decarboxylative Cross-Coupling

We report the Cu-promoted oxidative cross-coupling of α-fluoromalonate half-esters and aryl boron reagents to deliver mono-fluoro α-aryl acetates under mild conditions (in air at room temperature). The reaction uses a simple, readily available monofluorinated building block to generate arylated compounds with functional groups that are not easily tolerated by existing methods, such as aryl bromides, iodides, pyridines, and pyrimidines.

Nickel-Catalyzed Monofluoroalkylation of Arylsilanes via Hiyama Cross-Coupling

The first example of nickel-catalyzed monofluoroalkylation of arylsilanes has been developed with readily available fluoroalkyl halides. This novel transformation has demonstrated high reactivity, broad substrate scope, excellent functional group tolerance, and mild reaction conditions. The selective activation of a relatively inert C-Si bond for slow release of aryl carbanion is the key reason for reducing the amount of arylmetal species, which makes this method more promising for fluorine-containing modification of complex bioactive molecules. Mechanistic investigations indicate that a free fluoroalkyl radical is involved in this catalytic cycle.

Nickel-catalyzed monofluoromethylation of aryl boronic acids

Aryl boronic acids can be monofluoromethylated under nickel catalysis. The utility of this method is demonstrated by the monofluoromethylation of a borylated and acyl-protected derivative of the statin drug ezetimibe. Mechanistic investigations indicate that a fluoromethyl radical is involved in the NiI/NiIII catalytic cycle.

Palladium-catalyzed cross-coupling of ethyl α-bromo-α- fluoroacetate with arylboronic acids: Facile synthesis of α-aryl-α- fluoroacetate

Palladium-catalyzed Suzuki-Miyaura coupling reactions of ethyl α-bromo-α-fluoroacetate with various structurally diverse arylboronic acids using a phosphine ligand proceeded smoothly to afford α-aryl-α-fluoroacetate in moderate to good yields. This method provides a practical and efficient route to diverse α-monofluorinated α-arylcarbonyl compounds. Georg Thieme Verlag Stuttgart New York.

Electrochemical partial fluorination of phenylacetic acids esters and 1-tetralone

Anodic oxidation of some benzyl derivatives (phenylacetic acids esters) 1, and 1-tetralone 4, using ammonium fluorides or ammonium tetrafluoroborate as fluorine sources and supporting electrolytes and CH2Cl2 as solvent, allowed the i

FLUORINATION OF AROMATIC α-HYDROXYESTERS WITH N,N-DIETHYL-1,1,2,3,3,3-HEXAFLUOROPROPANEAMINE

The reaction of N,N-diethyl-1,1,2,3,3,3-hexafluoropropaneamine (PPDA) with aromatic α-hydroxyesters exchanged F for OH and gave their corresponding fluorides.For example, ethyl 2-fluoro-2-(p-tolyl) acetate was obtained from the reaction of ethyl 2-hydroxy-2-(p-tolyl) actate with PPDA.

MONO ET DIFLUORATION ELECTROCHIMIQUES DE GROUPES BENZYLIQUES

Anodic oxidation of benzylic compounds 1 using CH3CN as a solvent and Et3N,3HF as a fluorinating reagent allowed to introduce a fluorine atom in α position of electron withdrawing group via carbocation 1+ (ECBECN mechanism).Whatever the E group, monofluorides 2 are obtained in good yields from paramethoxy derivatives 1 (R=p-OCH3).In this case, by raising the potential of working electrode after the monofluorination step, gem difluorides 3 can be directly prepared from 1.When the substituent of the phenyl ring is different of a methoxy group, a mixture of fluoride 2 and acetamide 4 is generally obtained and the ratio of these two compounds is related to cation stability.