160001-85-4

Usage

Physical state

Colorless liquid

Odor

Strong

Uses

a. Solvent in pharmaceutical and agrochemical production
b. Precursor in organic synthesis
c. Production of specialty chemicals, pesticides, and commercial products
d. Potential use in medical imaging
e. Potential treatment for certain medical conditions

Reactivity

High

Safety concerns

Health and environmental risks if not properly managed

Upstream product

• 81290-20-2 (trifluoromethyl)trimethylsilane 
• 123324-71-0 p-tert-butylphenylboronic acid 
• 887144-97-0 Togni's reagent 
• 402-43-7 p-trifluoromethylphenyl bromide 
• 677-22-5 tert-butylmagnesium chloride 
• 147531-11-1 trifluoromethanesulfonic acid diphenyl(trifluoromethyl)sulfonium salt 
• 2314-97-8 iodotrifluoromethane 
• 77152-08-0 trifluoromethylcopper(I) 
• 75-46-7 trifluoromethan 
• 3972-65-4 1-bromo-4-tert-butylbenzene 
• 2926-29-6 Langlois reagent 
• 154318-75-9 4-tert-butylphenyl triflate 
• 35779-04-5 1-tert-butyl-4-iodobenzene 
• 1214756-50-9 2-cyclopropyl-1-(trifluoromethyl)benzo[b]thiophenium triflate 

Relevant academic research and scientific papers

Copper-mediated trifluoromethylation of arylboronic acids by trifluoromethyl sulfonium salts

The ligand-free trifluoromethylation of arylboronic acids with a [Ph 2SCF3]+[OTf]-/Cu(0) system has been carefully investigated. Aryl-, alkenyl- and heteroarylboronic acids with a variety of functional groups were suitable substrates for this reaction. It is suggested that a CuCF3 species is formed under the reaction conditions.

Isolation and characterization of copper(III) trifluoromethyl complexes and reactivity studies of aerobic trifluoromethylation of arylboronic acids

The isolation, characterization and reactivity of transition metal trifluoromethyl complexes are fundamental and challenging topics in trifluoromethylation chemistry. We report herein the synthesis and isolation of two new complexes [(phen)CuI(PPh3)2]+[CuIII(CF3)4]- (2) and (phen)CuIII(CF3)3 (3) as well as a known complex (bpy)CuIII(CF3)3 (4) at room temperature. 2 and 3 have been fully characterized using 1H, 19F, 31P NMR, elemental analyses and X-ray crystallography. Reactivity studies indicate that 2 is unreactive toward arylboronic acids. In contrast, 3 and 4 can react with various aryl and heteroaryl boronic acids to deliver trifluoromethylated arenes in good to quantitative yields under mild conditions. The presence of a fluoride additive in DMF under aerobic conditions is crucial to these reactions. This study provides fundamental information about the structure and reactivity of elusive Cu(iii) trifluoromethyl complexes that have been proposed as relevant reactive intermediates in many trifluoromethylation reactions.

DBU-Promoted Trifluoromethylation of Aryl Iodides with Difluoromethyltriphenylphosphonium Bromide

DBU-promoted trifluoromethylation of aryl iodides with difluoromethyltriphenylphosphonium bromide (DFPB) in the presence of copper source is described. In this transformation, DBU not only acts as base to deprotonate the difluoromethyl group in DFPB to generate difluoromethylene phosphonium ylide Ph3P+CF2-, but also converts the difluorocarbene generated from ylide Ph3P+CF2- into trifluoromethyl anion, finally resulting in the trifluoromethylation of aryl iodides. The reactions proceeded smoothly to afford expected products in moderate to good yields.

-and [Ni(CF3)4]2-: Foundations toward the Development of Trifluoromethylations at Unsupported Nickel

Nickel anions [(MeCN)Ni(CF3)3]- and [Ni(CF3)4]2- were prepared by the formal addition of 3 and 4 equiv, respectively, of AgCF3 to [(dme)NiBr2] in the presence of the [PPh4]+ counterion. Detailed insights into the electronic properties of these new compounds were obtained through the use of density functional theory (DFT) calculations, spectroscopy-oriented configuration interaction (SORCI) calculations, X-ray absorption spectroscopy, and cyclic voltammetry. The data collectively show that trifluoromethyl complexes of nickel, even in the most common oxidation state of nickel(II), are highly covalent systems whereby a hole is distributed on the trifluoromethyl ligands, surprisingly rendering the metal to a physically more reduced state. In the cases of [(MeCN)Ni(CF3)3]- and [Ni(CF3)4]2-, these complexes are better physically described as d9 metal complexes. [(MeCN)Ni(CF3)3]- is electrophilic and reacts with other nucleophiles such as phenoxide to yield the unsupported [(PhO)Ni(CF3)3]2- salt, revealing the broader potential of [(MeCN)Ni(CF3)3]- in the development of ligandless trifluoromethylations at nickel. Proof-in-principle experiments show that the reaction of [(MeCN)Ni(CF3)3]- with an aryl iodonium salt yields trifluoromethylated arene, presumably via a high-valent, unsupported, and formal organonickel(IV) intermediate. Evidence of the feasibility of such intermediates is provided with the structurally characterized [PPh4]2[Ni(CF3)4(SO4)], which was derived through the two-electron oxidation of [Ni(CF3)4]2-.

Ligand-dependent formation of ion-pair CuI/CuIII trifluoromethyl complexes containing bisphosphines

We report novel ion-pair bisphosphine CuI/CuIII trifluoromethyl complexes [(P2)2CuI]+[CuIII(CF3)4]- (P2 = DPPE, BINAP or Xantphos) fea

Copper-catalyzed trifluoromethylation of aryl and vinyl boronic acids with an electrophilic trifluoromethylating reagent

Chemical equations presented. A copper-catalyzed trifluoromethylation of aryl- and alkenylboronic acids with Tognis reagent was described. The reaction proceeded in good to excellent yields for a range of different substrates including heteroarylboronic acids and substrates with a variety of functional groups under mild reaction conditions.

Dual Nickel/Photoredox-Catalyzed Deaminative Cross-Coupling of Sterically Hindered Primary Amines

We report a method to activate α-3° amines for deaminative arylation via condensation with an electron-rich aldehyde and merge this reactivity with nickel metallaphotoredox to generate benzylic quaternary centers, a common motif in pharmaceuticals and natural products. The reaction is accelerated by added ammonium salts. Evidence is provided in support of two roles for the additive: inhibition of nickel black formation and acceleration of the overall reaction rate. We demonstrate a robust scope of amine and haloarene coupling partners and show an expedited synthesis of ALK2 inhibitors.

Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents**

The acetonitrile-solvated [(MeCN)Ni(C2F5)3]? was prepared in order to compare and contrast its reactivity with the known [(MeCN)Ni(CF3)3]? towards organic electrophiles. Both [(MeCN)Ni(CF3)3]? and [(MeCN)Ni(C2F5)3]? successfully react with aryl iodonium and diazonium salts as well as alkynyl iodonium salts to give fluoroalkylated organic products. Electrochemical analysis of [(MeCN)NiII(C2F5)3]? suggests that, upon electro-oxidation to [(MeCN)nNiIII(C2F5)3], reductive homolysis of a perfluoroethyl radical occurs, with the concomitant formation of [(MeCN)2NiII(C2F5)2]. Catalytic C?H trifluoromethylations of electron-rich arenes were successfully achieved using either [(MeCN)Ni(CF3)3]? or the related [Ni(CF3)4]2?. Stoichiometric reactions of the solvated nickel complexes reveal that “ligandless” nickel is exceptionally capable of serving as reservoir of CF3 groups under catalytically relevant conditions.

Site-Specific Alkene Hydromethylation via Protonolysis of Titanacyclobutanes

Methyl groups are ubiquitous in biologically active molecules. Thus, new tactics to introduce this alkyl fragment into polyfunctional structures are of significant interest. With this goal in mind, a direct method for the Markovnikov hydromethylation of alkenes is reported. This method exploits the degenerate metathesis reaction between the titanium methylidene unveiled from Cp2Ti(μ-Cl)(μ-CH2)AlMe2 (Tebbe's reagent) and unactivated alkenes. Protonolysis of the resulting titanacyclobutanes in situ effects hydromethylation in a chemo-, regio-, and site-selective manner. The broad utility of this method is demonstrated across a series of mono- and di-substituted alkenes containing pendant alcohols, ethers, amides, carbamates, and basic amines.

METHOD FOR PRODUCING PERFLUOROALKYLATED COMPOUND

Provided is a method for producing a perfluoroalkylated compound at low cost, safely and with high efficiency. A method for producing a perfluoroalkylated compound, comprising reacting a bis(perfluoroalkanoyl) peroxide with a compound having a carbon-carb