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Upstream product

• 5707-44-8 4-ethylbiphenyl 
• 420-43-9 1-bromo-1,1-difluoroethane 
• 3315-91-1 4-biphenylylmagnesium bromide 
• 92-91-1 biphenyl-4-acetaldehyde 
• 144432-80-4 2-(biphenyl-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 75-68-3 1-Chloro-1,1-difluoroethane 
• 1591-31-7 4-iodo-biphenyl 
• 2051-62-9 4'-biphenyl chloride 
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• 557-40-4 Allyl ether 
• 5122-94-1 4-biphenylboronic acid 
• 1276111-26-2 [1,1′-biphenyl]-4-yl(mesityl)iodonium trifluoromethanesulfonate 
• 115134-88-8 (1,1-difluoroethyl)trimethylsilane 
• 139214-48-5 2-(biphenyl-4-yl)-2-methyl-1,3-dithiane 

Relevant academic research and scientific papers

Iron-Catalyzed Fluoroalkylation of Arylborates with Sulfone Reagents: Beyond the Limitation of Reduction Potential

The iron-catalyzed alkyl–aryl coupling reaction between sulfones and arylboron compounds has remained a challenge. We report the first iron-catalyzed radical difluoroalkylation of arylborates with N-heteroaryl sulfones. The coordination between the iron catalyst and the nitrogen atom of N-heteroaryl sulfones was identified to be important in overcoming the reduction potential limitation of sulfones in the intermolecular single-electron-transfer process, which enables both fluoroalkyl N-heteroaryl sulfones (with relatively high reduction potentials) and nonfluorinated alkyl N-heteroaryl sulfones (with low reduction potentials) to serve as powerful alkylation reagents.

Visible-light photoredox-catalyzed selective carboxylation of C(sp3)?F bonds with CO2

It is highly attractive and challenging to utilize carbon dioxide (CO2), because of its inertness, as a nontoxic and sustainable C1 source in the synthesis of valuable compounds. Here, we report a novel selective carboxylation of C(sp3)?F bonds with CO2 via visible-light photoredox catalysis. A variety of mono-, di-, and trifluoroalkylarenes as well as α,α-difluorocarboxylic esters and amides undergo such reactions to give important aryl acetic acids and α-fluorocarboxylic acids, including several drugs and analogs, under mild conditions. Notably, mechanistic studies and DFT calculations demonstrate the dual role of CO2 as an electron carrier and electrophile during this transformation. The fluorinated substrates would undergo single-electron reduction by electron-rich CO2 radical anions, which are generated in situ from CO2 via sequential hydride-transfer reduction and hydrogen-atom-transfer processes. We anticipate our finding to be a starting point for more challenging CO2 utilization with inert substrates, including lignin and other biomass.

Reduction coupled method for synthesizing 1, 1- difluoroethyl aromatic compound

The introduction of 1,1 - difluoroethyl of, difluoroethyl aromatic compound through reduction coupling improves the metabolic stability .1,1 - of the biomolecules and therefore develops a new, difluoroethylating method which has an important meaning 1,1 - of. difluoro monochloroethane 1,1 - using cheap industrial raw materials. (CH3 CF2 Cl, Is known as Freon R142b,1kg/50 component), and the difluoroethylating reagent, realizes 1,1 - difluoro ethylating reaction, for realizing halogenated aromatic hydrocarbon under the catalytic action of transition metal nickel, and the yield is higher. to realize the synthesis of, difluoroethyl aromatic compound in a simple 1,1 - efficient manner.

Simple new synthesis method for 1,1-difluoroethyl aromatic compound

The invention particularly relates to a simple new synthesis method for a 1,1-difluoroethyl aromatic compound and belongs to the technical field of technology application of organic compounds. The 1,1-difluoroethyl modified molecules belong to a series of important bioactive molecules or medicine molecule precursors; by introducing the 1,1-difluoroethyl group, metabolic stability of biomolecules is improved. The invention, overcoming the defects of the prior art, discloses the new method for the first time, wherein low-cost and easy-to-obtain 1,1-difluorochloroethane (CH3CF2Cl, aka Freon R142b, 50 yuan/kg) is employed as a fluorine alkylation reagent, and under the effect of transition metal catalysts, such as nickel, the 1,1-difluoro-ethylation reaction of arylboronic acid is achieved. The method can achieve synthesis of the 1,1-difluoroethyl aromatic compound easily and high-effectively.

1,1-Difluoroethyl chloride (CH3CF2Cl), a novel difluoroalkylating reagent for 1,1-difluoroethylation of arylboronic acids

1,1-Difluoroethylated aromatics are of great importance in medicinal chemistry and related fields. 1,1-Difluoroethyl chloride (CH3CF2Cl), a cheap and abundant industrial raw material, is viewed as an ideal 1,1-difluoroethylating reagent, but the direct introduction of the difluoroethyl (CF2CH3) group onto aromatic rings using CH3CF2Cl has not been successfully accomplished. Herein, we disclose a nickel-catalyzed 1,1-difluoroethylation of arylboronic acids with CH3CF2Cl for the synthesis of (1,1-difluoroethyl)arenes.

Bulky Diamine Ligand Promotes Cross-Coupling of Difluoroalkyl Bromides by Iron Catalysis

Although iron-catalyzed cross-coupling of Grignard reagents with alkyl halides has been well established, the adoption of the reaction for fluoroalkylations has not been reported because traditional catalytic systems often lead to defluorination reactions. Described herein is the investigation of an iron-catalyzed cross-coupling between arylmagnesium bromides and difluoroalkyl bromides with modified N,N,N′,N′-tetramethyl-ethane-1,2-diamine (TMEDA) as a ligand. The use of this bulky diamine, in which a butylene is substituted at one carbon atom of the ethylene backbone in TMEDA, enables the iron-catalyzed difluoroalkylation under mild reaction conditions with a wide range of difluoroalkyl bromides, including vulnerable bromodifluoromethane, thus providing a general and cost-efficient route for applications in medicinal chemistry.

Radical C-H Fluorination Using Unprotected Amino Acids as Radical Precursors

We report a unique example of utilizing unprotected amino acids for benzylic C-H fluorination via a radical process. α-Aminoalkyl radicals are readily generated via oxidative decarboxylation of unprotected amino acids using a simple silver(I) catalyst and Selectfluor, which serves as both a mild oxidant and source of electrophilic fluorine. Mechanistic investigation shows that coordination of the unprotected amino acid plays a crucial role in lowering the oxidation potential of Ag(I), enabling oxidation under mild conditions. Mono- or difluorination is possible by controlling the stoichiometry of amino acid and fluorine source.

METHOD FOR PRODUCING (FLUOROALKYL) ARENE

PROBLEM TO BE SOLVED: To provide a method for efficiently producing fluoroalkyl arene, which is important as synthetic raw materials for medicines and functional materials. SOLUTION: A fluoroalkyl arene is produced by the reaction between an aryl metal species represented by formula (2) and a fluoroalkyl halide represented by formula (3) in the presence of a cobalt compound and an ethylenediamine derivative. In the formula (2) shown in the following figure, R11-R15 independently represent H, a C1-C4 alkyl group or the like. In the formula (3): Y-Rf, Y is Cl or the like; Rf is a C2-C3 fluoroalkyl group. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT

Copper-Mediated Aromatic 1,1-Difluoroethylation with (1,1-Difluoroethyl)trimethylsilane (TMSCF2CH3)

A new method for the formation of 1,1-difluoroethyl copper species (“CuCF2CH3”) with 1,1-difluoroethylsilane (TMSCF2CH3) has been developed. The “CuCF2CH3” species can be applied to the efficient 1,1-difluoroethylation of diaryliodonium salts under mild conditions, affording (1,1-difluoroethyl)arenes in good to excellent yields. This convenient procedure tolerates a wide range of functional groups and thus serves as a practical synthetic tool for the introduction of CF2CH3 group(s) into complex molecules.

Cobalt/diamine-catalyzed 1,1-difluoroethylation and 2,2,2-trifluoroethylation of aryl Grignard reagents with corresponding fluoroalkyl halides

Cobalt/diamine-catalyzed 1,1-difluoroethylation and 2,2,2-trifluoroethylation of aryl Grignard reagents with 1,1-difluoroethyl and 2,2,2-trifluoroethyl halides were investigated. With regard to the 1,1-difluoroethylation, 1,2-bis(dimethylamino)-2-methylpropane, which has been rarely used in the cross-coupling reactions, gave the highest yield among the diamine ligands tested. In the 2,2,2-trifluoroethylation, trans-1,2-bis(dimethylamino)cyclohexane provided the desired products in satisfactory yields with not only 2,2,2-trifluoroethyl iodide but also chloride. This Co/diamine catalyst was also effective for the coupling with other partially fluorinated alkyl halides in the presence of appropriate diamine ligands.