329-17-9

Upstream product

• 455-14-1 4-trifluoromethylphenylamine 
• 74-88-4 methyl iodide 
• 50-00-0 formaldehyd 
• 623-26-7 terephthalonitrile radical anion 
• 75-63-8 Bromotrifluoromethane 
• 121-69-7 N,N-dimethyl-aniline 
• 55642-42-7 bis(trifluoromethyl)tellurium 
• 402-43-7 p-trifluoromethylphenyl bromide 
• 67530-30-7 N,N-dimethyl O-(2,4,6-trimethylphenyl-sulfonyl) hydroxylamine 
• 1092380-21-6 S-(trifluoromethyl)-4-nitrophenylphenylsulfonium tetrafluoroborate 
• 1226-46-6 thiomichlersketone 
• 1092380-24-9 S-(trifluoromethyl)-4-nitrophenylphenylsulfonium triflate 
• 698-70-4 4-Iodo-N,N-dimethylaniline 
• 99-98-9 4-amino-N,N-dimethylaniline 

Downstream Products

• 125541-95-9 N,N-Dimethyl-N-ethyl-4-(trifluoromethyl)anilinium p-toluenesulfonate 
• 50-00-0 formaldehyd 
• 22864-65-9 N-methyl-4-(trifluoromethyl)aniline 
• 524-38-9 N-hydroxyphthalimide 
• 1246260-87-6 N,N,N-trimethyl-4-(trifluoromethyl)benzeneaminium trifluoromethanesulfonate 
• 1456524-31-4 2-(methyl(4-(trifluoromethyl)phenyl)amino)-1-phenylethanone 
• 402-54-0 p-nitrobenzotrifluoride 
• 1369856-62-1 2-bromo-N,N-dimethyl-4-(trifluoromethyl)aniline 

Relevant academic research and scientific papers

Visible-Light-Mediated Late-Stage Sulfonylation of Anilines with Sulfonamides

A visible-light-mediated late-stage sulfonylation of anilines with sulfonamides under simple reaction conditions is presented. Various primary or secondary sulfonamides including several pharmaceuticals were incorporated successfully via N–S bond activati

Aminomethylation of Aryl Bromides by Nickel-Catalyzed Electrochemical Redox Neutral Cross Coupling

We develop an electrochemical nickel-catalyzed aminomethylation of aryl bromides under mild conditions. The convergent paired electrolysis makes full use of anode and cathode processes, free of a terminal oxidant, a sacrificial anode, a metal reductant, and a prefunctionalized radical precursor. In addition, this method exhibits wide functional group tolerance (63 examples), including some sensitive substituents and aromatic heterocycles. This redox neutral cross coupling provides a more environmentally friendly and synthetic practical protocol for forging C(sp2)–C(sp3) bonds.

Borane-Trimethylamine Complex as a Reducing Agent for Selective Methylation and Formylation of Amines with CO2

We report herein that a borane-trimethylamine complex worked as an efficient reducing agent for the selective methylation and formylation of amines with 1 atm CO2 under metal-free conditions. 6-Amino-2-picoline serves as a highly efficient catalyst for the methylation of various secondary amines, whereas in its absence, the formylation of primary and secondary amines was achieved in high yield with high chemoselectivity. Mechanistic studies suggest that the 6-amino-2-picoline-borane catalytic system operates like an intramolecular frustrated Lewis pair to activate CO2.

Mechanistic Insight into Copper-Mediated Trifluoromethylation of Aryl Halides: The Role of CuI

The synthesis, characterization, and reactivity of key intermediates [Cu(CF3)(X)]-Q+ (X = CF3 or I, Q = PPh4) in copper-mediated trifluoromethylation of aryl halides were studied. Qualitative and quantitative studies showed [Cu(CF3)2]-Q+ and [Cu(CF3)(I)]-Q+ were not highly reactive. Instead, a much more reactive species, ligandless [CuCF3] or DMF-ligated species [(DMF)CuCF3], was generated in the presence of excess CuI. On the basis of these results, a general mechanistic map for CuI-promoted trifluoromethylation of aryl halides was proposed. Furthermore, on the basis of this mechanistic understanding, a HOAc-promoted protocol for trifluoromethylation of aryl halides with [Ph4P]+[Cu(CF3)2]- was developed.

Nickel-Catalyzed Amination of Aryl Chlorides with Amides

A nickel-catalyzed amination of aryl chlorides with diverse amides via C-N bond cleavage has been realized under mild conditions. A broad substrate scope with excellent functional group tolerance at a low catalyst loading makes the protocol powerful for synthesizing various aromatic amines. The aryl chlorides could selectively couple to the amino fragments rather than the carbonyl moieties of amides. Our protocol complements the conventional amination of aryl chlorides and expands the usage of inactive amides.

Coupling of Alternating Current to Transition-Metal Catalysis: Examples of Nickel-Catalyzed Cross-Coupling

The coupling of transition-metal to photoredox catalytic cycles through single-electron transfer steps has become a powerful tool in the development of catalytic processes. In this work, we demonstrated that transition-metal catalysis can be coupled to al

Trialkylammonium salt degradation: Implications for methylation and cross-coupling

Trialkylammonium (most notably N,N,N-trimethylanilinium) salts are known to display dual reactivity through both the aryl group and the N-methyl groups. These salts have thus been widely applied in cross-coupling, aryl etherification, fluorine radiolabelling, phase-transfer catalysis, supramolecular recognition, polymer design, and (more recently) methylation. However, their application as electrophilic methylating reagents remains somewhat underexplored, and an understanding of their arylation versus methylation reactivities is lacking. This study presents a mechanistic degradation analysis of N,N,N-trimethylanilinium salts and highlights the implications for synthetic applications of this important class of salts. Kinetic degradation studies, in both solid and solution phases, have delivered insights into the physical and chemical parameters affecting anilinium salt stability. 1H NMR kinetic analysis of salt degradation has evidenced thermal degradation to methyl iodide and the parent aniline, consistent with a closed-shell SN2-centred degradative pathway, and methyl iodide being the key reactive species in applied methylation procedures. Furthermore, the effect of halide and non-nucleophilic counterions on salt degradation has been investigated, along with deuterium isotope and solvent effects. New mechanistic insights have enabled the investigation of the use of trimethylanilinium salts in O-methylation and in improved cross-coupling strategies. Finally, detailed computational studies have helped highlight limitations in the current state-of-the-art of solvation modelling of reaction in which the bulk medium undergoes experimentally observable changes over the reaction timecourse. This journal is

Photon-initiated heterogeneous redox couples for methylation of anilines under mild conditions

Methylation of anilines has drawn a lot of attention due to their valuable applications and directly using methanol as a methylation reagent is of great advantage. Photon-initiated heterogeneous catalysis of this methylation process meets the requirements of green chemistry. Herein we show that balanced redox zones within carbon nitride supported Pd nanoparticles boost the selectivity of methylation of anilines under mild conditions.

Zinc Powder Catalysed Formylation and Urealation of Amines Using CO2 as a C1 Building Block?

Transformation of CO2 into valuable organic compounds catalysed by cheap and biocompatible metal catalysts is one of important topics of current organic synthesis and catalysis. Herein, we report the zinc powder catalysed formylation and urealation of amines with CO2 and (EtO)3SiH under solvent free condition. Using 2 molpercent zinc powder as the catalyst, a series of secondary amines, both the aromatic ones and the aliphatic ones, can be formylated into formamides. When primary aromatic amines were used as the substrates, the reactions produce urea derivatives. The electronic and steric effects from the substrates on the formylation and urealation reactions were observed and discussed. The recovery and reusability of zinc powder were investigated, showing the zinc powder can be reused in the formylation reaction without loss of catalytic activity. The analysis on the reactants/products mixture after filtering out the zinc powder showed the zinc concentration in the mixture is low to 1 ppm. The pathways for the formylation and urealation of amines with this catalytic system were also investigated, and related to the different substrates.

Three-Component Aminoselenation of Arynes

The three-component coupling of tertiary amines, arynes, and aryl selenium bromide or diaryl diselenide as an electrophilic selenium source allowing the synthesis of 2-selanyl aniline derivatives is reported. This aminoselenation reaction of arynes installs a C-N and C-Se bond under mild conditions, and the products are formed in moderate to good yields. This reaction is compatible with various functional groups, and the preliminary studies on the mechanism of the reaction is also provided.