4409-83-0

Upstream product

• 4294-57-9 para-methylphenylmagnesium bromide 
• 106-38-7 para-bromotoluene 
• 599-00-8 trifluoroacetic acid-d₁ 
• 624-31-7 4-tolyl iodide 
• 811-98-3 d⁽⁴⁾-methanol 
• 108-88-3 toluene 
• 53188-52-6 1-(methylsulfonyl)-2-(4-methylphenyl)diazene 
• 1177-35-1 2,4,6-Tris(4-methylphenoxy)-1,3,5-triazine 
• 13277-99-1 4-methylbenzaldehyde-α-d₁ 
• 60565-88-0 bis(4-methylphenyl)iodonium hexafluorophosphate 
• 121-45-9 phosphorous acid trimethyl ester 
• 50-00-0 formaldehyd 
• 459-44-9 4-methylbenzenediazonium tetrafluoroborate 
• 2417-95-0 p-tolyllithium 

Downstream Products

• 106-44-5 p-cresol 
• 33836-85-0 4-deuterated benzaldehyde 
• 116467-71-1 C₇H₇⁽²⁾HO 
• 115943-93-6 2-deuterio-4-methylphenol 
• 13122-27-5 4-deuterobenzyl alcohol 
• 116467-72-2 C₇H₇⁽²⁾HO 
• 77765-18-5 [4-²H]benzyl bromide 
• 108-39-4 3-methyl-phenol 
• 614-34-6 p-cresyl benzoate 
• 623-11-0 1-methyl-4-nitrosobenzene 
• 108-88-3 toluene 
• 90625-42-6 trans-4,4'-dideuterio-stilbene 
• 36696-80-7 <4-²H>benzyl cyanide 
• 66223-91-4 <4-²H>phenylacetic acid 

Relevant academic research and scientific papers

ALKYLATED TROPYLIUM IONS-III. (13)C NMR SPECTRA OF METHYLATED TROPYLIUM IONS, CORRELATIONS AMONG (1)H AND (13)C CHEMICAL SHIFTS, AND ELECTRON DENSITY BY THE HUECKEL MO METHOD.

The (13)C NMR spectra for all seventeen methylated tropylium ions have been obtained in acetonitrile-d3 and the chemical shifts of the Me- and the ring-carbons assigned.The plots of the (13)C shifts of ring-carbons against charge densities calc

Electrocatalytic Deuteration of Halides with D2O as the Deuterium Source over a Copper Nanowire Arrays Cathode

Precise deuterium incorporation with controllable deuterated sites is extremely desirable. Here, a facile and efficient electrocatalytic deuterodehalogenation of halides using D2O as the deuteration reagent and copper nanowire arrays (Cu NWAs) electrochemically formed in situ as the cathode was demonstrated. A cross-coupling of carbon and deuterium free radicals might be involved for this ipso-selective deuteration. This method exhibited excellent chemoselectivity and high compatibility with the easily reducible functional groups (C=C, C≡C, C=O, C=N, C≡N). The C?H to C?D transformations were achieved with high yields and deuterium ratios through a one-pot halogenation–deuterodehalogenation process. Efficient deuteration of less-active bromide substrates, specific deuterium incorporation into top-selling pharmaceuticals, and oxidant-free paired anodic synthesis of high-value chemicals with low energy input highlighted the potential practicality.

Nickel-catalysed C–O bond reduction of 2,4,6-triaryloxy-1,3,5-triazines in 2-methyltetrahydrofuran

A nickel-catalysed reduction of phenol derivatives activated by 2,4,6-trichloro-1,3,5-triazine (TCT) in ecofriendly 2-methyltetrahydrofuran (2-MeTHF) is described. The phenol-TCT derivatives were readily prepared using grinding method in short time without further purification. This catalytic system allowed the facile C–O cleavage of phenol-TCT derivatives under mild reaction conditions with high efficiency and good functional group tolerance. Gram-scale reaction was also achieved. Particularly, sequential functionalization of phenol-TCT derivatives followed by C–O bond reduction could also be realized, affording the high value-added products in moderate to good yields.

Hydro/deutero deamination of arylazo sulfones under metal and (photo)catalyst-free conditions

Hydrodeaminated and monodeuterated aromatics were obtained via a visible-light driven reaction of arylazo sulfones. Deuteration occurs efficiently in deuterated media such as isopropanol-d8 or in THF-d8/water mixtures and exhibits a high tolerance to the nature and the position of the aromatic substituents.

Palladium-Catalyzed Deformylation Reactions with Detailed Experimental and in Silico Mechanistic Studies

A facile, efficient, and general deformylation reaction with a wide-ranging functional group compatibility has been developed with palladium acetate as a precatalyst under exogenous ligand-free conditions. The mechanistic details of the palladium-catalyzed deformylation reaction have been outlined on the basis of a combination of experimental and computational studies. The heterogeneous pathway is predominant for the deformylation, and homogeneous catalysis occurs to a lesser extent. This ligand-free catalytic cycle is proposed to undergo oxidative addition, migratory extrusion, and reductive elimination as the key steps. Kinetic studies reveal a first-order rate dependency with respect to the aldehyde. Furthermore, kinetic isotope effects, competition experiments, and Hammett studies suggest that the migratory extrusion step is the rate-determining step. For the homogeneous pathway, the experimental findings are also supported by DFT studies.

Metal-Free sp2-C-H Borylation as a Common Reactivity Pattern of Frustrated 2-Aminophenylboranes

C-H borylation is a powerful and atom-efficient method for converting affordable and abundant chemicals into versatile organic reagents used in the production of fine chemicals and functional materials. Herein we report a facile C-H borylation of aromatic and olefinic C-H bonds with 2-aminophenylboranes. Computational and experimental studies reveal that the metal-free C-H insertion proceeds via a frustrated Lewis pair mechanism involving heterolytic splitting of the C-H bond by cooperative action of the amine and boryl groups. The adapted geometry of the reactive B and N centers results in an unprecedentently low kinetic barrier for both insertion into the sp2-C-H bond and intramolecular protonation of the sp2-C-B bond in 2-ammoniophenyl(aryl)- or -(alkenyl)borates. This common reactivity pattern serves as a platform for various catalytic reactions such as C-H borylation and hydrogenation of alkynes. In particular, we demonstrate that simple 2-aminopyridinium salts efficiently catalyze the C-H borylation of hetarenes with catecholborane. This reaction is presumably mediated by a borenium species isoelectronic to 2-aminophenylboranes.

Direct Hydroxylation of Benzene to Phenol Using Hydrogen Peroxide Catalyzed by Nickel Complexes Supported by Pyridylalkylamine Ligands

Selective hydroxylation of benzene to phenol has been achieved using H2O2 in the presence of a catalytic amount of the nickel complex [NiII(tepa)]2+ (2) (tepa = tris[2-(pyridin-2-yl)ethyl]amine) at 60°C. The maximum yield of phenol was 21% based on benzene without the formation of quinone or diphenol. In an endurance test of the catalyst, complex 2 showed a turnover number (TON) of 749, which is the highest value reported to date for molecular catalysts in benzene hydroxylation with H2O2. When toluene was employed as a substrate instead of benzene, cresol was obtained as the major product with 90% selectivity. When H218O2 was utilized as the oxidant, 18O-labeled phenol was predominantly obtained. The reaction rate for fully deuterated benzene was nearly identical to that of benzene (kinetic isotope effect = 1.0). On the basis of these results, the reaction mechanism is discussed.

Chemo- and regioselective direct hydroxylation of arenes with hydrogen peroxide catalyzed by a divanadium-substituted phosphotungstate

Peroxide in, phenol out: The catalyst [-PW10O38V 2(μ-OH)2]3- showed high activity in the hydroxylation of various aromatic compounds with aqueous H2O 2. The system was regioselective, producing para-phenols from monosubstituted benzene derivatives. Furthermore, alkylarenes with reactive side-chain Ca spa 3-H bonds could be chemoselectively hydroxylated without significant formation of side-chain oxygenated products. Copyright

Tert-butoxide-mediated arylation of benzene with aryl halides in the presence of a catalytic 1,10-phenanthroline derivative

Sodium tert-butoxide mediates the coupling of aryl halides with benzene derivatives without the aid of transition metal catalysts but with a catalytic 1,10-phenanthroline derivative.

Stoichiometric and catalytic H/D incorporation by cationic iridium complexes: A common monohydrido-iridium intermediate

A mechanistic study of the Stoichiometric and catalytic H/D exchange reactions involving cationic iridium complexes is presented. Strong evidence suggests that both Stoichiometric and catalytic reactions proceed via a monohydrido-iridium species. Stoichiometric deuterium incorporation reactions introduce multiple deuterium atoms into the organic products when aryliridium compounds Cp*PMe3Ir(C6H4X)(OTf) (X = H, o-CH3, m-CH3, p-CH3) react with D2. Multiple deuteration occurs at the unhindered positions (para and meta) of toluene, when X = CH3. The multiple-deuteration pathway is suppressed in the presence of an excess of the coordinating ligand, CH3CN. The compound Cp*PMe3IrH(OTf) (1-OTf) is observed in low-temperature, Stoichiometric experiments to support a monohydrido-iridium intermediate that is responsible for catalyzing multiple deuteration in the stoichiometric system. When paired with acetone-d6, [Cp*PMe3IrH3][OTf] (4) catalytically deuterates a wide range of substrates with a variety of functional groups. Catalyst 4 decomposes to [Cp*PMe3Ir(η3-CH 2C(OH)CH2)][OTf] (19) in acetone and to [Cp*PMe 3IrH(CO)]-[OTf] (1-CO) in CH3OH. The catalytic H/D exchange reaction is not catalyzed by simple H+ transfer, but instead proceeds by a reversible C-H bond activation mechanism.