396-44-1

Usage

Type of compound

Tetrakis(trifluoromethyl) derivative of biphenyl

Physical state at room temperature

White solid

Solubility in water

Insoluble

Usage

Building block in organic synthesis

Applications

Production of pharmaceuticals, agrochemicals, and specialty chemicals

Chemical and physical properties

Imparts unique properties due to tetrakis(trifluoromethyl) group

Thermal and chemical stability

High, making it suitable as a flame retardant

Additional uses

Production of polymers and plastics as a flame retardant

Upstream product

• 328-70-1 3,6-bis(trifluoromethyl)bromobenzene 
• 200956-32-7 1-(benzyloxy)-2-bromo-4-(trifluoromethyl)benzene 
• 73852-19-4 3,5-bis-trifluromethylphenylboronic acid 
• 2830-53-7 1-(benzyloxy)-2-bromo-4-methylbenzene 
• 123-31-9 hydroquinone 
• 2797-28-6 lithium tetrakis(pentafluorophenyl)borate 
• 79060-88-1 sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate 
• 15522-59-5 tetrabutylammonium tetraphenylborate 
• 17984-89-3 triethoxy(thiophen-2-yl)silane 
• 328-73-4 3,5-bis(trifluoromethyl)iodobenzene 
• 90-11-9 1-Bromonaphthalene 

Downstream Products

• 402-31-3 1,3-bis(trifluoromethyl)benzene 
• 478930-63-1 [Pt(bis(di-tert-butylphosphino)methane)(η2-(3,5,3',5'-tetrakis(trifluoromethyl)biphenyl))] 

Relevant academic research and scientific papers

Electrochemical instability of highly fluorinated tetraphenyl borates and syntheses of their respective biphenyls

Highly fluorinated tetraphenyl borate anions are of importance as weakly coordinating anions in metalorganic reactions. However, at high positive potentials their electrochemical stability in organic solvents is not sufficient. This was investigated by a comprehensive cyclic voltammetry study and can be used synthetically to generate highly fluorinated biphenyls.

Electrochemical Synthesis of Biaryls via Oxidative Intramolecular Coupling of Tetra(hetero)arylborates

We report herein versatile, transition metal-free and additive-free (hetero)aryl-aryl coupling reactions promoted by the oxidative electrocoupling of unsymmetrical tetra(hetero)arylborates (TABs) prepared from ligand-exchange reactions on potassium trifluoroarylborates. Exploiting the power of electrochemical oxidations, this method complements the existing organoboron toolbox. We demonstrate the broad scope, scalability, and robustness of this unconventional catalyst-free transformation, leading to functionalized biaryls and ultimately furnishing drug-like small molecules, as well as late stage derivatization of natural compounds. In addition, the observed selectivity of the oxidative coupling reaction is related to the electronic structure of the TABs through quantum-chemical calculations and experimental investigations.

Defluorinative functionalization of Pd(II) fluoroalkyl complexes

When subjected to arylboranes, anionic trifluoromethyl and difluorobenzyl palladium(II) complexes undergo fluoride abstraction followed by 1,1-migratory insertion. The resulting intermediate fluoroalkyl species can be induced to undergo a subsequent transmetalation and reductive elimination from either an in situ formed fluoroboronate (FB(Ar3)-) or an exogenous boronic acid/ ester (ArB(OR)2) and nucleophilic activator, representing a net defluorinative arylation reaction. The latter method enabled a structurally diverse substrate scope to be prepared from either an isolated palladium-CF3 complex, or from Pd(PPh3)4 and other commercially available reagents.

Palladium-mediated radical homocoupling reactions: A surface catalytic insight

In this contribution, we report a palladium nanoparticle-promoted reductive homocoupling of haloarenes that proceeds efficiently to produce corresponding bis-aryls in moderate to excellent yields using relatively low catalyst loading (1 mol%), and exhibits broad functional group tolerance. This work sheds light on how the surface state of Pd(0) nanoparticles plays a crucial role in the reactivity of catalytic systems. Notably, the appropriate choice of palladium salts for the preparation of the preformed nanocatalysts was a key parameter having a major impact on the catalytic activity; thus, the effect of halide anions on the reactivity of the as-prepared palladium nanoparticles could be assessed, with iodide anions being capable of inhibiting the corresponding homocoupling reaction. The homocoupling reaction mechanism has been further studied by means of radical trap and electron paramagnetic resonance (EPR) experiments, revealing that the reaction proceeds via radical intermediates. Taking into account these data, a plausible reaction mechanism based on single-electron transfer processes on the palladium nanoparticle surface is discussed.

Oxidative and Reductive Cross-Coupling Reactions Catalyzed by an Anionic "ligandless" Palladium Complex

The anionic complex [NBu4][Pd(DMSO)Cl3], which can be synthesized on a gram scale in a single step starting from commercially available starting materials, has been shown to be an active catalyst in the Mizoroki-Heck reaction of aryl halides. We present two new catalytic applications of this complex: the base-free oxidative Heck reaction and the reductive homodimerization of aryl halides. This complex outperformed other palladium salts. In the latter reaction, the catalyst loading could be reduced to 0.01 mol %. The scope of the reactions has been explored, demonstrating the potential of the anionic palladium complex in these catalytic transformations.

Copper-catalyzed Hiyama coupling of (hetero)aryltriethoxysilanes with (hetero)aryl iodides

A CuI-catalyzed Hiyama coupling was achieved, which proceeds in the absence of an ancillary ligand for aryl-heteroaryl and heteroaryl-heteroaryl couplings. A P,N-ligand is required to obtain the best product yields for aryl-aryl couplings. In addition to facilitating transmetalation, CsF is also found to function as a stabilizer of the [CuAr] species, potentially generated as an intermediate after transmetalation of aryltriethoxysilanes with Cu I-catalysts in the absence of ancillary ligands.

Palladium catalytic systems with hybrid pyrazole ligands in C-C coupling reactions. Nanoparticles versus molecular complexes

This paper reports the comparison of the chemoselectivity of two different Pd catalytic systems, namely molecular and colloidal systems, in C-C coupling reactions. For this purpose, new hybrid pyrazole derived ligands containing alkylether, alkylthioether or alkylamino moieties have been synthesized and used to form Pd(ii) complexes and to stabilize Pd nanoparticles (Pd NPs). With the aim of studying the coordination mode of the ligands and further to understand their role in catalysis, both types of Pd species were characterized by appropriate techniques. In C-C coupling reactions promoted by different Pd colloidal systems, several reports evidenced that active species are molecular catalysts leached from Pd NPs. The most important feature of this work relies on the differences observed in the output of C-C coupling reactions, depending on the colloidal or molecular nature of the catalyst employed. Thus, molecular systems carry out typical Suzuki-Miyaura cross-coupling, together with the dehalogenation of the substrate in different proportions. In contrast, Pd NPs catalyze either Suzuki-Miyaura or C-C homocoupling reactions depending on the haloderivative used. Interestingly, Pd NPs catalyze the quantitative dehalogenation of 4-iodotoluene. Differences observed in the chemoselectivity of these two catalytic systems support that reactions carried out with Pd NPs stabilized with the hybrid pyrazole ligands employed here take place on the surface of the colloids. The Royal Society of Chemistry 2013.

Novel biphenyl organocatalysts for iminium ion-catalyzed asymmetric epoxidation

Two novel chiral biphenyl iminium salts derived from L-acetonamine, containing electron-withdrawing 3,30-substituents on the biphenyl unit, have been prepared and tested as asymmetric catalysts for epoxidation of prochiral alkenes. The results are compared with those achieved using the corresponding unsubstituted system.

2,4-Bis(fluorocarbon)-substituted phenols for high yield Newman-Kwart rearrangement reactions

The Newman-Kwart thermal rearrangement of two 2,4-disubstituted O-arylthiocarbamates, prepared from the corresponding phenols, is reported. Clean conversion to the S-arylthiocarbamates in high yields was observed. The rearrangement appears to be facilitat

A state-of-the-art cyanation of aryl bromides: A novel and versatile copper catalyst system inspired by nature

A general protocol for the cyanation of aryl halides with the nontoxic cyanide source K4[Fe(CN)6] using copper catalysis and a ligand system based on 1-alkylimidazoles is presented. The advantages of this system are the high selectivity, a unique substrate range, easy handling, and inexpensive reagents.