2802-98-4

Upstream product

• 83-13-6 diethyl 2-phenylmalonate 
• 128812-96-4 perfluoro- 
• 28744-77-6 sodium diethyl-2-phenylmalonate 
• 126543-35-9 (Z)-3-Ethoxy-2-phenyl-3-trimethylsilanyloxy-acrylic acid ethyl ester 
• 643-77-6 fluoro-phenyl-acetic acid ethyl ester 
• 541-41-3 chloroformic acid ethyl ester 
• 107263-95-6 N-fluoropyridinium triflate 
• 107263-98-9 N-fluoro-2,6-dimethylpyridinium triflate 
• 130433-77-1 N-fluoro-4-tert-butylpyridinium triflate 
• 108-86-1 bromobenzene 
• 685-88-1 fluoromalonic acid diethyl ester 
• 4870-65-9 2-bromophenylacetic acid 
• 2882-19-1 ethyl 2-phenyl-2-bromoacetate 
• 591-50-4 iodobenzene 

Downstream Products

• 1547-97-3 fluoro-phenyl-malonic acid diamide 
• 1578-63-8 d'acide 2-fluoro-2-phenyl acetique 
• 1578-78-5 α-fluoro-α-phenylmalonic acid 
• 211506-10-4 monoethyl 2-fluoro-2-phenylmalonate 
• 211506-14-8 2-fluoro-2-phenyl-1,3-propanediol 
• 233277-18-4 ethyl 2-fluoro-3-hydroxy-2-phenylpropanoate 
• 233277-24-2 3-(t-butyldimethylsilyloxy)-2-fluoro-2-phenyl-1-propanol 
• 63818-95-1 S(+)-acide fluoro-2 phenyl-2 acetique 
• 63818-94-0 (R)-α-fluoro-α-phenylacetic acid 
• 233277-33-3 ethyl 2-fluoro-2-phenyl-3-(p-toluenesulfonyloxy)propanoate 
• 233277-26-4 2-fluoro-3-(triisopropylsilyloxy)-2-phenyl-1-propanol 
• 233277-23-1 ethyl 3-(benzyloxy)-2-fluoro-2-phenylpropanoate 

Relevant academic research and scientific papers

Electrophilic Fluorination with N-Fluoroquinuclidinium Fluoride

N-Fluoroquinuclidinium fluoride (NFQNF), obtainable in ca. 90percent yield by direct low-temperature liquid-phase fluorination of quinuclidine, has been used to deliver 'positive' fluorine to carbanionic sites in a number of organic substrates.

N-Halogeno compounds. Part 15. Synthesis of N-fluoroquinuclidinium salts via direct fluorination of quinuclidine-Lewis acid adducts, and a comparison of their "F+" transfer capabilities

Fluorine smoothly attacks quinuclidine-trifluoroborane, quinuclidine-pentafluorophosphorane, and quinuclidine-sulfur trioxide in acetonitrile at -35 °C to give the corresponding N-fluoroquinuclidinium salts NFQ+X- (X- =BF4-, PF6-, and FSO3- respectively; Q = quinuclidine). Like its tetrafluoroborate analogue (NFQ+BF4-), the hexafluorophosphate NFQ+PF6- can also be prepared by direct fluorination of quinuclidine in the presence of the appropriate sodium salt (NaPF6). An alternative route to the tetrafluoroborate involves treatment of NFQ+F- with boron trifluoride. A comparative study of site-specific electrophilic fluorination of methoxybenzene [ → 1-fluoro2-and 4-methoxybenzene], 2-hydroxynaphthalene ( → 1-fluoro-2-hydroxynaphthalene and 1,1-difluoro-2-oxo-1,2-dihydronaphthalene), 2-nitropropan-2-yl-lithium ( → 2-fluoro-2-nitropropane) and diethyl sodio (phenyl) malonate [ → diethyl fluoro(phenyl) malonate] with all of the NFQ+X- salts mentioned above, plus the triflate (X- = CF3SO3-), revealed that the hexafluorophosphate and triflate are the most easily-handled and effective reagents.

A Unified and Desymmetric Approach to Chiral Tertiary Alkyl Halides

Enantioenriched tertiary alkyl halides are prevalent in bioactive molecules and can serve as versatile synthetic intermediates to construct complex structures. While conventional access to these motifs often hinges on stereoselective carbon-halogen or carbon-carbon bond formation reactions, desymmetric approaches using halogenated and prochiral tetrasubstituted carbons are largely elusive in comparison. Here, we report that a suite of dinuclear zinc catalysts with a prolinol- or pipecolinol-derived tetradentate ligand can reductively desymmetrize a large collection of easily available halomalonic esters to α-halo-β-hydroxyesters. These polyfunctionalized tertiary alkyl fluorides, chlorides, and bromides proved to be useful intermediates toward fluorinated drug analogs and polyhalogenated monoterpenes. The facile intramolecular epoxidation of the chiral chloride and bromide products has also enabled expeditious access to natural products containing tertiary alcohol motifs.

Methyl NFSI: Atom-economical alternative to NFSI shows higher fluorination reactivity under Lewis acid-catalysis and non-catalysis

Me-NFSI was first reported in 1994. Despite its atom-economical structure and similarity to a well-explored fluorinating reagent, NFSI, Me-NFSI has not appeared in the literature in over 20 years. We disclose that Me-NFSI is more effective for the fluorination of active methines under Lewis acid-catalysis and non-catalysis than NFSI.

Methods for synthesis of dicarbamate compounds and intermediates in the formation thereof

Disclosed is a method of making 2-substituted-2-halo-1,3-propanediols via reduction of corresponding malonate compounds. Also disclosed is a method of making 2-substituted-2-halo-1,3-dicarbamate compounds (such as halo derivatives of felbamate, including fluorofelbamate) via reduction of malonate compounds, followed by carbamoylation. Reduction of the malonate compounds is carried out using an electrophilic hydride reagent.

Palladium-catalyzed arylation of malonates and cyanoesters using sterically hindered trialkyl- and ferrocenyldialkylphosphine ligands

Palladium-catalyzed reactions of aryl bromides and chlorides with two common stabilized carbanions - enolates of dialkyl malonates and alkyl cyanoesters - are reported. An exploration of the scope of these reactions was conducted, and the processes were shown to occur in a general fashion. Using P(t-Bu)3 (1), the pentaphenylferrocenyl ligand (Ph5C5)Fe(C5H4)P(t-Bu) 2 (2), or the adamantyl ligand (1-Ad)P(t-Bu)2 (3), reactions of electron-poor and electron-rich, sterically hindered and unhindered aryl bromides and chlorides were shown to react with diethyl malonate, di-tertbutyl malonate, diethyl fluoromalonate, ethyl cyanoacetate, and ethyl phenylcyanoacetate. Although alkyl malonates and ethyl alkylcyanoacetates did not react with aryl halides using these catalysts, the same products were formed conveniently in one pot from diethylmalonate by cross-coupling of an aryl halide in the presence of excess base and subsequent alkylation.

Preparative-scale enzyme-catalyzed synthesis of (R)-α-fluorophenylacetic acid

A preparative-scale asymmetric synthesis of (R)-α-fluorophenylacetic acid, a useful chiral derivatizing reagent, is described. Starting from ethyl α-bromophenylacetate, α-fluorophenylmalonic acid dipotassium salt was prepared in three steps (54% yield), including nucleophilic substitution by the fluoride ion as the keystep. Both the purified form and crude preparation of arylmalonate decarboxylase in E. coli worked well on this substrate, and (R)-α-flurophenylacetic acid (>99% e.e.) was prepared in a quantitative yield.

Chemoenzymatic synthesis of 2-substituted 2-fluoro-1,3-dioxygenated chiral building blocks

A series of 2-substituted-2-fluoro-1,3-dioxygenated chiral building blocks are synthesized via a chemoenzymatic route using either (i) lipase catalyzed monohydrolysis of suitably functionalized malonic diesters, or (ii) lipase catalyzed monoacetylation of suitably functionalized 1,3-propanediols.

N-fluorosulfonimides, process for their production, as well as their use as fluorinating agents

N-fluorosulfonimides of general formula I in which R1 means a methyl group each or together a group --(CH2)n --with n=1, 2 or 3, especially N-flouromethanesulfonimide, (CH3 SO2)2 NF, their production as well as their use for electrophilic fluorination of activated C--H bonds of organic molecules, are described.

Synthesis of 2-Substituted 2-Arylmalonates via Tricarbonylchromium Complexes

Tricarbonylchromium complexes 1 react with monosubstituted malonic acid esters 2 in DMSO at room temperature in the presence of KOtBu to give the complexes 3. After oxidative demetalation, the appropriate aryl derivatives 4 are obtained in moderate to good overall yields. Diastereoselective arylations of chirally modified malonates such as 5a-c were studied. The stereoselectivity was highest for the products 6c/6c′ (80:20) with (-)-8-phenylmenthol as alcohol component in the malonate 5.