89100-22-1

Upstream product

• 128796-39-4 4-trifluoromethylphenylboronic acid 
• 555-16-8 4-nitrobenzaldehdye 
• 636-98-6 p-nitrobenzene iodide 
• 201230-82-2 carbon monoxide 
• 402-43-7 p-trifluoromethylphenyl bromide 
• 122-04-3 4-nitro-benzoyl chloride 
• 199620-14-9 chromium⁽⁰⁾ hexacarbonyl 
• 1096047-96-9 4-nitrophenyl(4-(trifluoromethyl)phenyl)methanol 
• 52898-51-8 N-methoxy-N-methyl-4-nitrobenzamide 
• 135325-18-7 methyl 2-(4-(trifluoromethyl)phenyl)acetate 
• 98-95-3 nitrobenzene 

Relevant academic research and scientific papers

C(acyl)-C(sp2) and C(sp2)-C(sp2) Suzuki-Miyaura cross-coupling reactions using nitrile-functionalized NHC palladium complexes

Application of N-heterocyclic carbene (NHC) palladium complexes has been successful for the modulation of C-C coupling reactions. For this purpose, a series of azolium salts (1a-f) including benzothiazolium, benzimidazolium, and imidazolium, bearing a CN-substituted benzyl moiety, and their (NHC)2PdBr2 (2a-c) and PEPPSI-type palladium (3b-f) complexes have been systematically prepared to catalyse acylative Suzuki-Miyaura coupling reaction of acyl chlorides with arylboronic acids to form benzophenone derivatives in the presence of potassium carbonate as a base and to catalyse the traditional Suzuki-Miyaura coupling reaction of bromobenzene with arylboronic acids to form biaryls. All the synthesized compounds were fully characterized by Fourier Transform Infrared (FTIR), and 1H and 13C NMR spectroscopies. X-ray diffraction studies on single crystals of 3c, 3e and 3f prove the square planar geometry. Scanning Electron Microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), metal mapping analyses and thermal gravimetric analysis (TGA) were performed to get further insights into the mechanism of the Suzuki-Miyaura cross coupling reactions. Mechanistic studies have revealed that the stability and coordination of the complexes by the CN group are achieved by the removal of pyridine from the complex in catalytic cycles. The presence of the CN group in the (NHC)Pd complexes significantly increased the catalytic activities for both reactions.

Dirhodium-Catalyzed Enantioselective B?H Bond Insertion of gem-Diaryl Carbenes: Efficient Access to gem-Diarylmethine Boranes

The scarcity of reliable methods for synthesizing chiral gem-diarylmethine borons limits their applications. Herein, we report a method for highly enantioselective dirhodium-catalyzed B?H bond insertion reactions with diaryl diazomethanes as carbene precursors. These reactions afforded chiral gem-diarylmethine borane compounds in high yield (up to 99 % yield), high activity (turnover numbers up to 14 300), high enantioselectivity (up to 99 % ee) and showed unprecedented broad functional group tolerance. The borane compounds synthesized by this method could be efficiently transformed into diaryl methanol, diaryl methyl amine, and triaryl methane derivatives with good stereospecificity. Mechanistic studies suggested that the borane adduct coordinated to the rhodium catalyst and thus interfered with decomposition of the diazomethane, and that insertion of a rhodium carbene (generated from the diaryl diazomethane) into the B?H bond was most likely the rate-determining step.

Systematic Evaluation of 1,2-Migratory Aptitude in Alkylidene Carbenes

Alkylidene carbenes undergo rapid inter- and intramolecular reactions and rearrangements, including 1,2-migrations of β-substituents to generate alkynes. Their propensity for substituent migration exerts profound influence over the broader utility of alkylidene carbene intermediates, yet prior efforts to categorize 1,2-migratory aptitude in these elusive species have been hampered by disparate modes of carbene generation, ultrashort carbene lifetimes, mechanistic ambiguities, and the need to individually prepare a series of 13C-labeled precursors. Herein we report on the rearrangement of 13C-alkylidene carbenes generated in situ by the homologation of carbonyl compounds with [13C]-Li-TMS-diazomethane, an approach that obviates the need for isotopically labeled substrates and has expedited a systematic investigation (13C{1H} NMR, DLPNO-CCSD(T)) of migratory aptitudes in an unprecedented range of more than 30 alkylidene carbenes. Hammett analyses of the reactions of 26 differentially substituted benzophenones reveal several counterintuitive features of 1,2-migration in alkylidene carbenes that may prove of utility in the study and synthetic application of unsaturated carbenes more generally.

Synthesis, structure, and characterization of picolyl- and benzyl-linked biphenyl palladium N-heterocyclic carbene complexes and their catalytic activity in acylative cross-coupling reactions

N-heterocyclic carbene ligands with picolyl (L1H2Br2, L3H2Br2) and benzyl (L2H2Br2, L4H2Br2) linked biphenyl backbone were synthesized and characterized. Their palladium(II) complexes [PdL1]Br2 (1), [PdL2Br2] (2), [PdL3]Br2 (3), and [PdL4Br2] (4) were synthesized by direct method using Pd(OAc)2. All complexes (1–4) were characterized by CHN analysis, electrospray ionization-MS, nuclear magnetic resonance, and single-crystal X-ray diffraction. Molecular structures confirm the distorted square planar geometry around the Pd(II) center. All of them showed good catalytic activity in acylative Suzuki cross coupling of phenyl boronic acid with benzoyl chloride to afford benzophenone in good yields.

Binuclear Palladium Complex Immobilized on Mesoporous SBA-16: Efficient Heterogeneous Catalyst for the Carbonylative Suzuki Coupling Reaction of Aryl Iodides and Arylboronic Acids Using Cr(CO)6 as Carbonyl Source

Abstract: In this study, a binuclear palladium complex immobilized on the organo-functionalized SBA-16 was prepared and structurally characterized by routine techniques. Characterizations indicated that the mesostructure of SBA-16 was maintained after the immobilization of palladium complex. Then, the prepared nanomaterial was applied as a heterogeneous catalyst in the carbonylative Suzuki coupling reaction of aryl iodides with arylboronic acids using Cr(CO)6 as carbonyl source. The catalyst was efficiently promoted the coupling reactions of various aryl iodides and arylboronic acids to give the corresponding diaryl ketones in excellent yields. Moreover, the catalyst was readily recovered by filtration and could be reused for seven cycles without losing its structural integrity and catalytic activity. Graphic Abstract: [Figure not available: see fulltext.].

Aerobic oxidative acylation of nitroarenes with arylacetic esters under mild conditions: Facile access to diarylketones

A facile and regioselective base-mediated aerobic oxidative acylation of nitroarenes to access diarylketones under mild conditions has been developed. It features the use of bench-stable and readily available arylacetates as acyl surrogates, and the absence of transition-metals and synthetic oxidants. This protocol involves a cascade CDC/oxidative decarboxylation process.

Diarylketone preparation method

The invention discloses a diarylketone preparation method. According to the method, substituted nitrobenzene and aromatic acetic ester are dissolved in an organic solvent, alkali is added, the mixture is subjected to a reaction in the air or oxygen atmosphere at the temperature of 10-60 DEG C for 0.5-24 h, and diarylketone is obtained; the mole ratio of substituted nitrobenzene to aromatic acetic ester is (0.5:1)-(5:1), and the mole ratio of alkali to aromatic acetic ester is (1:1)-(5:1). The method overcomes defects caused by the adoption of strong acid or expensive metal reagents or strong oxidizers and the like in the prior art and has the advantages as follows: 1) with air as an oxidizer, use of strong or expensive chemical oxidizers is avoided; 2) no transition metal catalysts are used, so that the condition that heavy metal ions are left in a product is avoided; 3) without inductive groups, surplus steps of introduction of the inductive groups and removal of the inductive groups are avoided; 4) acylation of ortho positions or para positions of nitro-aromatic compounds is directly realized, which cannot be realized with a classic Friedel-Crafts acylation method. The synthesis method plays an important role in preparing diarylketone, particularly industrial production of acylation products of ortho positions or para positions of the nitro-aromatic compounds.

Base free Suzuki acylation reactions of sodium (aryl trihydroxyborate) salts: A novel synthesis of substituted aryl ketones

The first simple and efficient base free Pd(PPh3)4 catalysed synthesis of substituted aryl ketones from acyl chlorides and easily accessible sodium aryl trihydroxyborate salts in aqueous toluene is reported. The reaction conditions appeared versatile and tolerable to a variety of functional groups including, CF3, OMe, SMe, Br, NO2, F, OH and NH2 furnishing 25 examples of substituted aryl ketones in isolated yields of up to 96% in 24 h. Beside the high purity, the ease and convenience of the isolation compared to boronic acids, sodium aryl trihydroxyborate salts could be used subsequently without the addition of excess amount of an activator and are more user-friendly in terms of the use of accurate reaction stoichiometry.

In situ generation of palladium nanoparticles: Ligand-free palladium catalyzed pivalic acid assisted carbonylative Suzuki reactions at ambient conditions

Highly selective carbonylative Suzuki reactions of aryl iodides with arylboronic acids using an in situ generated nanopalladium system furnished products in high yields. The reactions were performed under ambient conditions and in the absence of an added ligand. The key to success is the addition of pivalic acid, which can effectively suppress undesired Suzuki coupling. The synthesis can be easily scaled up, and the catalytic system can be reused up to nine times. The nature of the active catalytic species are discussed.

In situ generated nickel nanoparticle-catalyzed carbonylative Suzuki reactions of aryl iodides with arylboronic acids at ambient CO pressure in poly(ethylene glycol)

A general in situ generated nickel nanoparticle-catalyzed carbonylative Suzuki reactions of aryl iodides with arylboronic acids at atmospheric CO pressure in poly(ethylene glycol) has been demonstrated. A wide range of aryl iodides and arylboronic acids can be coupled to the corresponding biarylketones with high yields even in the absence of an added ligand and at low catalyst loading. The nature of the active catalytic species is discussed. This journal is