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• 20912-50-9 4-benzoylbenzaldehyde 
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• 1137-41-3 (4-aminophenyl)(phenyl)methanone 
• 611-95-0 4-carboxybenzophenone 
• 39148-58-8 4-benzoylbenzoyl chloride 
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• 1438388-96-5 tributyl(difluoromethyl)stannane 
• 6136-66-9 4-iodobenzophenone 
• 275818-95-6 sodium difluoromethanesulfinate 

Relevant academic research and scientific papers

Decarbonylative Fluoroalkylation at Palladium(II): From Fundamental Organometallic Studies to Catalysis

This Article describes the development of a decarbonylative Pd-catalyzed aryl-fluoroalkyl bond-forming reaction that couples fluoroalkylcarboxylic acid-derived electrophiles [RFC(O)X] with aryl organometallics (Ar-M′). This reaction was optimized by interrogating the individual steps of the catalytic cycle (oxidative addition, carbonyl de-insertion, transmetalation, and reductive elimination) to identify a compatible pair of coupling partners and an appropriate Pd catalyst. These stoichiometric organometallic studies revealed several critical elements for reaction design. First, uncatalyzed background reactions between RFC(O)X and Ar-M′ can be avoided by using M′ = boronate ester. Second, carbonyl de-insertion and Ar-RF reductive elimination are the two slowest steps of the catalytic cycle when RF = CF3. Both steps are dramatically accelerated upon changing to RF = CHF2. Computational studies reveal that a favorable F2C-H - -X interaction contributes to accelerating carbonyl de-insertion in this system. Finally, transmetalation is slow with X = difluoroacetate but fast with X = F. Ultimately, these studies enabled the development of an (SPhos)Pd-catalyzed decarbonylative difluoromethylation of aryl neopentylglycol boronate esters with difluoroacetyl fluoride.

Electrochemical-Promoted Nickel-Catalyzed Oxidative Fluoroalkylation of Aryl Iodides

This work describes a general strategy for metal-catalyzed cross-coupling of fluoroalkyl radicals with aryl halides under electrochemical conditions. The contradiction between anodic oxidation of fluoroalkyl sulfinates and cathodic reduction of low-valent nickel catalysts can be well addressed by paired electrolysis, allowing for direct introduction of fluorinated functionalities into aromatic systems.

Palladium-Catalyzed Decarbonylative Difluoromethylation of Acid Chlorides at Room Temperature

Methods for the direct synthesis of difluoromethylated arenes are sparse, despite the importance of the difluoromethyl group in medical, agro-, and materials chemistry. A palladium-catalyzed decarbonylative cross-coupling reaction of acid chlorides with a difluoromethyl zinc reagent is achieved to access difluoromethylated compounds. The transformation proceeds at room temperature and shows broad functional group tolerance, thus providing a general and efficient method for decarbonylative difluoromethylation of a wide range of aromatic carboxylic acids.

Palladium-Catalyzed Difluoromethylation of Aryl Chlorides and Triflates and Its Applications in the Preparation of Difluoromethylated Derivatives of Drug/Agrochemical Molecules

A palladium-catalyzed difluoromethylation of a series of aryl chlorides and triflates under mild conditions was described. A variety of common functional groups were tolerated. In addition, by using this protocol, several drug molecules containing an aryl chloride unit were successfully difluoromethylated, thus enabling medicinal chemists to rapidly access novel drug derivatives with potentially improved properties via late-stage functionalization.

Metal-free18F-labeling of aryl-CF2H via nucleophilic radiofluorination and oxidative C-H activation

A metal-free and selective method to form [18F]aryl-CF2H through nucleophilic radiofluorination of benzyl (pseudo)halides and oxidative C-H activation of benzylic C-H bonds has been developed. The method is operationally simple and tolerates a variety of electron-neutral/deficient arenes and heteroarenes.

Transition-metal-free C-H oxidative activation: Persulfate-promoted selective benzylic mono- and difluorination

An operationally simple and selective method for the direct conversion of benzylic C-H to C-F to obtain mono- and difluoromethylated arenes using Selectfluor as a fluorine source is developed. Persulfate can be used to selectively activate benzylic hydrogen atoms toward C-F bond formation without the aid of transition metal catalysts.

Pd-catalyzed α-arylation of α,α-difluoroketones with aryl bromides and chlorides. A route to difluoromethylarenes

We report the Pd-catalyzed α-arylation of α,α- difluoroketones with aryl and heteroaryl bromides and chlorides catalyzed by an air- and moisture-stable palladacyclic complex containing P(t-Bu)Cy2 as ligand. The combination of this Pd-catalyzed arylation and base-induced cleavage of the acyl-aryl C-C bond within the α-aryl-α,α- difluoroketone constitutes a one-pot, two-step procedure to synthesize difluoromethylarenes from aryl halides. A broad range of electronically varied aryl and heteroaryl bromides and chlorides underwent these two transformations, providing α-aryl-α,α-difluoroketones, difluoromethylarenes, and difluoromethylheteroarenes in high yields.

METAL-CATALYZED COUPLING OF ARYL AND VINYL HALIDES WITH ALPHA, ALPHA-DIFLUOROCARBONYL COMPOUNDS

The coupling of aryl, heteroaryl, and vinyl halides with α,α-difluoroketones or silyl ethers or siylenol ethers of α,α-difluoroketones and α,α-difluoroamides and esters are described. Further derivatization of the coupling products (such as ketone cleavage and Baeyer-Villiger oxidation) is also described.

Sandmeyer difluoromethylation of (hetero-)arenediazonium salts

A Sandmeyer-type difluoromethylation process has been developed that allows the straightforward conversion of (hetero-)arenediazonium salts into the corresponding difluoromethyl (hetero-)arenes under mild conditions. The actual difluoromethylating reagent, a difluoromethyl-copper complex, is formed in situ from copper thiocyanate and TMS-CF2H. The diazonium salts are either preformed or generated in situ from broadly available aromatic amines.

Copper-mediated difluoromethylation of (hetero)aryl iodides and β-styryl halides with tributyl(difluoromethyl)stannane

Owing to their unique properties, molecules containing the difluoromethyl group (CF2H) are of great interest. Tributyl(difluoromethyl)stannane has now been used for the selective and efficient direct ipso difluoromethylation of aryl iodides, he