- Regioselective mononitration of biphenyl by use of stoichiometric quantities of nitrogen dioxide and molecular oxygen over rare earth cationexchanged β-Zeolite catalysts
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In the presence of molecular oxygen and zeolite La-b with Si/ Al2 = 260, regioselective mononitration of biphenyl with stoichiometric quantities of liquid nitrogen dioxide occurs at 20 °C to yield mononitrobiphenyl, as the main product, in yields up to 82.7 %. The 2-nitrobiphenyl:4-nitrobiphenyl isomer ratio is 0.34. The process is eco-friendly and inexpensive, and the zeolite is easily regenerated by simple work-up to give results similar to those obtained with the fresh catalyst.
- Tai, Yan Fang,Dong, Xiong Zi,Xu, Hao Shu,Shi, Chun Jie,Peng, Xin Hua
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Read Online
- Preparation and characterization of new palladium complex immobilized on (chitosan)/PoPD biopolymer and its catalytic application in Suzuki cross-coupling reaction
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The present work reports the design, synthesis, and characterization of palladium complex immobilized on chitosan/poly(o-phenylenediamine) (CS-PoPD-Pd) for the catalytic application in the Suzuki–Miyaura C-C cross-coupling reaction through a nontoxic, inexpensive, eco-friendly, and practical method. Fourier-transform–infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), elemental mapping, X-ray diffraction (XRD), and inductively coupled plasma-optical emission spectrometry (ICP-OES) techniques were used for analyzing the prepared catalyst. Characterization studies showed that CS-PoPD-Pd was successfully synthesized according to our design. CS-PoPD-Pd composite demonstrated high product yield and high turnover number (TON) and turnover frequency (TOF) values with small catalyst loading for the Suzuki–Miyaura C-C cross-coupling reaction under mild reaction conditions. Besides, the synthesized CS-PoPD-Pd composite could be readily recycled and reused for at least five runs without discernible loss of its catalytic activity.
- Seyedi, Neda,Zahedifar, Mahboobeh
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- Pd(II) and Ni(II) complexes containing ONNO tetradentate Schiff base ligand: Synthesis, crystal structure, spectral characterization, theoretical studies, and use of PdL as an efficient homogeneous catalyst for Suzuki–Miyaura cross-coupling reaction
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Two new palladium(II) and nickel(II) Schiff base complexes are prepared through the reaction of Pd(OAc)2 and Ni(OAc)2·4H2O with a tetradentate ONNO Schiff base, derived by condensing 4,5-dimethyl-1,2-phenylenediamine and 4-methoxysalicylaldehyde. The elemental analysis (CHN) and other spectroscopic techniques such as FT-IR and 1H NMR were used to characterize the synthesized ligand and its corresponding metal complexes. Moreover, the crystal structure of the Pd(II) complex was investigated by the single crystal X-ray diffraction analysis. The diffraction analysis explores a slightly distorted square planar geometry of the PdL complex due to the coordination with deprotonated phenolic O-atoms and N-atoms from azomethine chromophore. The DFT-based theoretical calculations which employed the B3LYP/Def2-TZVP level of theory explore that the theoretical results corresponded to the actual data obtained via spectroscopic characterization.
- Ashfaq, Muhammad,Bahadori, Mehrnaz,Behjatmanesh-Ardakani, Reza,Fallah-Mehrjardi, Mehdi,Kargar, Hadi,Moghadam, Majid,Munawar, Khurram Shahzad,Tahir, Muhammad Nawaz
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- Photoelectric properties of aromatic triangular tri-palladium complexes and their catalytic applications in the Suzuki-Miyaura coupling reaction
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The photoelectric properties and catalytic activities of substituted triphenylphosphine and sulfur/selenium ligand supported aromatic triangular tri-palladium complexes1-4, abbreviated as [Pd3]+, were investigated. The cyclic voltammogram of [Pd3]+in CH3CN-nBu4NPF6showed a single quasi-reversible wave which was consistent with their robust property and provided preliminary proof for their electron transfer processes in catalysis. With excitation at 267 nm, [Pd3]+exhibited strong ratiometric fluorescence at 550 and 780 nm at a temperature gradient from 77 K to 287 K. These peculiar triangular tri-palladium complexes showed excellent catalytic activities and exclusive reactivity with aryl iodides over the other halogenated aromatics in the Suzuki-Miyaura coupling reaction. The electronic and steric hindrance effects of substituents on the aryl iodides and aryl boronic acids including heteroaromatics like pyridine, pyrazine and thiophenes were explored and most substrates achieved up to 99% of yields. (2-[1,1′-Biphenyl]-2-ylbenzothiazole) which was analogous to the selective cyclooxygenase-2 (COX-2) inhibitors was also synthesized with our tri-palladium catalyst and gave good isolated yield (94%). The study of the catalytic process revealed that the mechanism of the reaction may involve the replacement of the sulphur ligand on [Pd3]+by iodine from aryl iodides, which was beneficial for the matching of C-I bond energy.
- Li, Jia,Li, Xujun,Liu, Xiang,Maestri, Giovanni,Malacria, Max,Wang, Xiaoshuang,Wang, Yanlan,Wu, Lingang
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supporting information
p. 11834 - 11842
(2021/09/06)
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- Nanocellulose Supported PdNPs as in situ Formed Nano Catalyst for the Suzuki Coupling Reaction in Aqueous Media: A Green Approach and Waste to Wealth
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An effective and highly sustainable method has been developed for the Suzuki coupling reaction of aryl halides and phenylboronic acid using in situ generated nacocellulose (NC) supported palladium nanoparticles (Pd@NC NPs) as heterogeneous catalysts in water. The formation of PdNPs was observed in the absence of additional reagents, during the course of the Suzuki reaction from NC and Pd(OAc)2. In situ formed Pd@NC NPs have been systematically characterized using TEM, EDX, XRD and FT-IR techniques. The in situ generated catalyst was separated and studied for its successful reusability up to 11 cycles. The application of aqueous media, use of in situ formed catalyst, mild reaction conditions, absence of volatile organic solvents, broad substrate scope, high product isolated yields are the significant developments of this protocol. The nanocellulose used for this protocol has been generated form the waste cotton cloth and hence it is an example for the waste to wealth and sustainable approach.
- Aabaka, Sreenath Reddy,Mao, Jincheng,Lavanya, Mallu,Venkateswarlu, Katta,Huang, Zhiyu,Mao, Jinhua,Yang, Xiaojiang,Lin, Chong
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supporting information
(2021/02/21)
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- NiFe2O4@SiO2@ZrO2/SO42-/Cu/Co nanoparticles: A novel, efficient, magnetically recyclable and bimetallic catalyst for Pd-free Suzuki, Heck and C-N cross-coupling reactions in aqueous media
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The novel heterogeneous bimetallic nanoparticles of Cu-Co were synthesized based on magnetic nanoparticles, and the magnetic nanocatalyst was characterized by XRD, FE-SEM, EDX mapping, BET, TEM, HRTEM, FTIR, TGA, and VSM. This catalyst was successfully applied as a recyclable magnetically catalyst in Heck, Suzuki, and C-N cross-coupling reactions with various aryl halides (iodides, bromides, and chlorides as challengeable substrates), with olefins, phenylboronic acid, and amines, respectively. We considered the rise of synergetic effects from the different Lewis acid and Br?nsted acid sites present in the catalyst. The catalyst was synthesized with cheap, available materials and a simple synthesis method. The catalyst can be separated easily using an external magnet. It was recycled for more than ten runs without a sensible loss of its catalytic activity, and no significant leaching of the Cu and Co quantity was observed. The significant benefits of the method are high-level generality, simple operation, and there are no heavy metals and toxic solvents. This is a quick, easy, efficacious and environmentally friendly protocol, and no by-products are formed in the reaction. These features make it an appropriate practical alternative protocol. In comparison with recent works, the other advantage of this catalyst is the synthesis of a wide variety of C-C and C-N bond derivatives (more than 40 derivatives). The other significant advantage is the low temperature of the reaction and the use of the least possible amount of the catalyst (0.003 g). The efficiency was good to excellent and the catalyst selectivity has been high. We aspire that our study inspires more interest to design novel catalysts based on using low-cost metal ions (such as cobalt and copper) in the cross-coupling reactions. This journal is
- Alavi G., Seyyedeh Ameneh,Nasseri, Mohammad Ali,Kazemnejadi, Milad,Allahresani, Ali,Hussainzadeh, Mahdi
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p. 7741 - 7757
(2021/05/13)
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- Pd(II) complexes with ONN pincer ligand: Tailored synthesis, characterization, DFT, and catalytic activity toward the Suzuki-Miyaura reaction
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A pincer type ONN tridentate Schiff base ligand, 2-(((pyridin-2-yl)methylimino)methyl)-6-methoxyphenol, (L1) synthesized by the condensation of 4-hydroxy-3-methoxy-benzaldehyde and (pyridin-2-yl)methanamine. The ligand L1 and the new Pd(II) heteroleptic complexes of the composition [Pd(L1)(L2)]Cl, where L2 = benzimidazole, imidazole, benzooxazol or pyridine were synthesized and characterized by a set of chemical, spectrometric and spectroscopic analyses. These complexes were named 1 to 4, respectively. The FT-IR and DFT have suggested that ligand is coordinated with metal through azomethine-N and phenolic-O and arranged in square planar fashion around the metal. Correlation coefficients value between 0.995 - 0.993 shows satisfactory agreement in theoretical and experimental 1H-NMR and 13C-NMR. Benzimidazole anchored complex 1 exhibits an excellent catalytic activity. DFT calculated the energy profile diagram of the Suzuki-Miyaura reaction.
- Bagri, Sanjay Singh,Chaurasia, Bhaskar,Gaur, Pratiksha,Mehrotra, Ripul,Raidas, Mohan Lal,Shukla, Satyendra Nath
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- Pd-Catalysed Suzuki-Miyaura cross-coupling of aryl chlorides at low catalyst loadings in water for the synthesis of industrially important fungicides
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The Suzuki-Miyaura coupling reaction of electron-poor aryl chlorides in the synthesis of crop protection-relevant active ingredients in water is disclosed. Optimisation of the reaction conditions allowed running the reaction with 50 ppm of Pd-catalyst loading without an additional organic solvent in the cross-coupling reaction step in short reaction times. The system was optimised for the initial cross-coupling step of the large scale produced fungicides Boscalid, Fluxapyroxad and Bixafen up to 97% yield. It is also shown that the Suzuki-Miyaura reaction can be easily scaled up to 50 g using a simple product separation and purification using environmentally benign solvents in the work-up. To show the usability of this method, it was additionally applied in the three-step synthesis of the desired active ingredients.
- Goetz, Roland,Hashmi, A. Stephen K.,Orecchia, Patrizio,Petkova, Desislava Slavcheva,Rominger, Frank,Schaub, Thomas
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supporting information
p. 8169 - 8180
(2021/11/01)
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- Non-c2-symmetric bis-benzimidazolium salt applied in the synthesis of sterically hindered biaryls
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A novel non-C2-symmetric bis-benzimidazolium salt derived from (±)-valinol has been prepared by a simple and straightforward process in good yield. The structure of bis-benzimidazolium salt provided a bulky steric group on the ethylene bridge; which facilitates the catalytic efficacy in the C(sp2 )–C(sp2 ) formation. Its catalytic activity in Suzuki–Miyaura cross-coupling reaction of unactivated aryl chlorides has been found to have high efficacy in 1 mol% Pd loading. This protocol demonstrated the potential on the synthesis of sterically hindered biaryls.
- Chen, Yen-Hsin,Hsu, Tung-Yu,Huang, Shu-Jyun,Hung, Pei-Yu,Lee, Dong-Sheng,Lu, Ta-Jung,Wei, Ting-Rong
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- NaI/PPh3-Mediated Photochemical Reduction and Amination of Nitroarenes
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A mild transition-metal- and photosensitizer-free photoredox system based on the combination of NaI and PPh3 was found to enable highly selective reduction of nitroarenes. This protocol tolerates a broad range of reducible functional groups such as halogen (Cl, Br, and even I), aldehyde, ketone, carboxyl, and cyano. Moreover, the photoredox catalysis with NaI and stoichiometric PPh3 provides also an alternative entry to Cadogan-type reductive amination when o-nitrobiarenes were used.
- Qu, Zhonghua,Chen, Xing,Zhong, Shuai,Deng, Guo-Jun,Huang, Huawen
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supporting information
p. 5349 - 5353
(2021/07/21)
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- Visible-light-driven Cadogan reaction
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Visible-light-driven photochemical Cadogan-type cyclization has been discovered. The organic D-A type photosensitizer 4CzIPN found to be an efficient mediator to transfer energy from photons to the transient intermediate that breaks the barriers of deoxygenation in Cadogan reaction and enables a mild metal-free access to carbazoles and related heterocycles. DFT calculation results indicate mildly endergonic formation of the intermediate complex of nitrobiarenes and PPh3, which corresponds with experimental findings regarding reaction temperature. The robust synthetic capacity of the photoredox Cadogan reaction systems has been demonstrated by the viable productivity of a broad range of carbazoles and related N-heterocycles with good tolerance of various functionalities.
- Qu, Zhonghua,Wang, Pu,Chen, Xing,Deng, Guo-Jun,Huang, Huawen
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supporting information
p. 2582 - 2586
(2021/03/09)
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- Polydopamine-Encapsulated Dendritic Organosilica Nanoparticles as Amphiphilic Platforms for Highly Efficient Heterogeneous Catalysis in Water
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Aqueous heterogeneous catalysis is a green, sustainable catalytic process that attracts increasing attention, but it often suffers from poor mass transfer, substrate adsorption and catalyst dispersion. Herein, we synthesized a type of amphiphilic core-shell catalysts with a hydrophilic polydopamine (PDA) shell and a hydrophobic dendritic organosilica nanoparticle (DON) core for heterogeneous catalysis in water. The hydrophilic shell allowed the catalyst dispersing well in water, and the hydrophobic core facilitated the absorption of organic reactants. The hierarchical core-shell structure facilitated rational arrangement of the location of catalytic species to match the reaction sequence. The obtained metal, enzyme and metal-enzyme amphiphilic catalysts demonstrated improved stability, selectivity and activity in aqueous reactions, including Pd-catalyzed cross-couplings (Suzuki, Liebeskind-Srogl, Heck and Sonogashira), enzymatic enantioselective reduction, chemoenzymatic cascade synthesis of chiral compounds and chemoenzymatic cascade degradation of organophosphates. The amphiphilic catalysts could be easily in situ recovered, and their high catalytic performance was sustained for five cycles.
- Gao, Jing,Guo, Na,Jiang, Yanjun,Liu, Guanhua,Liu, Pengbo,Liu, Yunting,Wang, Zihan,Zhang, Lei
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supporting information
p. 1975 - 1982
(2021/06/09)
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- Build-up of double carbohelicenes using nitroarenes: Dual role of the nitro functionality as an activating and leaving group
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The construction of double carbohelicenes is highly fascinating yet challenging work. Disclosed herein is a streamlined and simplified synthetic route to double carbohelicenes starting from nitroarenes through sequential nitro-activated ortho-C-H arylation, denitrative alkenylation and intramolecular cyclodehydrogenation. In this synthetic strategy, the nitro group plays a dual role namely as a leaving group for the denitrative alkenylation and as an activating group for ortho-C-H arylation, which is distinct from those of aryl halides in a conventional coupling reaction. In this work, the palladium-catalyzed Heck-type alkenylation of nitroarenes has been presented, in which the conventionally inert Ar-NO2 bond is cleaved. This work provides a novel synthetic strategy for polycyclic aromatic hydrocarbons (PAHs). This journal is
- Su, Rongchuan,Yang, Yudong,You, Jingsong,Zhou, Fujian,Zhou, Fulin
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p. 7424 - 7428
(2020/09/09)
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- Palladium-catalyzed denitrative Sonogashira-type cross-coupling of nitrobenzenes with terminal alkynes
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Described herein is a palladium-catalyzed cross-coupling reaction between nitroarenes and terminal alkynes, offering a facile method for C(sp2)-C(sp) bond formation. The utility of this protocol has been proven by the construction of polycyclic aromatic hydrocarbons (PAHs) and orthogonal cross-coupling.
- Feng, Boya,Yang, Yudong,You, Jingsong
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supporting information
p. 790 - 793
(2020/01/29)
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- L-lysine-Pd Complex Supported on Fe3O4 MNPs: a novel recoverable magnetic nanocatalyst for Suzuki C-C Cross-Coupling reaction
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In this work, L-lysine-Pd Complex, immobilized onto the surface of Fe3O4 MNPs, was successfully prepared via simple and inexpensive procedure. The prepared nanocatalyst was considered as a robust and clean nano-reactor catalyst for the Suzuki and Heck C-C Cross-Coupling reactions in water as the green condition. This eco-friendly heterogeneous catalyst was characterized by Fourier transform infrared spectroscopy (FT-IR), X-Ray Diffractometer (XRD), energy-dispersive X-ray spectroscopy (EDS), inductively coupled plasma atomic emission spectroscopy (ICP), X-ray mapping, BET, thermogravimetric analysis (TGA), vibrating sample magnetometer (VSM), scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) techniques. The use of a green medium, easy separation and workup, excellent reusability of the nanocatalyst and short reaction time are some outstanding advantages of this method.
- Ashraf, Muhammad Aqeel,Liu, Zhenling,Zhang, Dangquan,Alimoradi, Ashkan
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- Synthesis, characterization, crystal structure and catalytic activity of amido azo palladium(II) complex
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Abstract: The newly designed tridentate ligand, 2-((2-aminophenyl)diazenyl)-N-benzylaniline, 1 has been synthesized by the reaction between 2,2′-diaminoazobenzene and benzyl chloride in presence of K2CO3. This ligand was reacted with Na2[PdCl4] in methanol to give the new Pd(II) complex?2. Both the ligand and complex were characterized by usual spectroscopic techniques. Furthermore, the solid-state structure of complex 2 was determined using single crystal X-ray diffraction analysis. It revealed that the ligand binds with Pd(II) in dianionic tridentate (N,N,N) fashion offering distorted square planar geometry where fourth position is occupied by one phosphine ligand. The performance of the Pd(II) phosphine complex as catalyst was evaluated in the homogenous Suzuki and Heck reactions under mild conditions in presence of air and moisture. The Pd(II) complex showed good catalytic activities for the coupling of several aryl halides (iodides and bromides) with phenyl boronic acid and styrene providing excellent yields. After catalytic reactions, the catalyst has been recovered by simple chromatographic separation and reused for next reaction and its activity checked up to three cycles without sufficient loss. Graphic abstract: The newly designed tridentate ligand, 2-((2-aminophenyl)diazenyl)-N-benzylaniline and its corresponding palladium(II) complex were synthesized and structurally characterized. The neutral palladium(II) amido complex with phosphine as ancillary ligand was formed through two amino proton elimination from ligand precursor. The newly synthesized Palladium(II) complex acts as potential catalyst toward C–C bond formation for a variety of substrate under mild conditions in presence of air and moisture.[Figure not available: see fulltext.].
- Pratihar, Jahar Lal,Mandal, Paritosh,Mal, Dasarath,Lin, Chia-Her
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p. 553 - 559
(2020/06/22)
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- A Co-Cu bimetallic magnetic nanocatalyst with synergistic and bifunctional performance for the base-free Suzuki, Sonogashira, and C-N cross-coupling reactions in water
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A novel magnetically recyclable bimetallic catalyst was prepared by anchoring imidazolium moiety and PEG chains on Fe3O4 NPs and named as Fe3O4?PEG/Cu-Co. It was found to be a powerful catalyst for the Sonogashira, Suzuki, and C-N cross-coupling reactions in water as a green solvent without the need for any external base. Fe3O4?PEG/Cu-Co was well characterized with FT-IR, FE-SEM, TEM, VSM, EDX, ICP, UV-visible, CV, and XPS analyses. Optimum ranges of parameters such as time, temperature, and amount of catalyst were investigated by Design-Expert 10.0.7 software for C-C Suzuki, Sonogashira, and C-N cross-coupling reactions to find the optimum conditions. The catalyst was compatible with a variety of aryl halides and N-arenes and gave favorable coupling products with good to high yields for all of them. Hot filtration and Hg poisoning tests involving the nanocatalyst revealed the stability, low metal leaching, and heterogeneous nature of the catalyst. Reaction mechanisms were proposed by study of the UV-visible spectra in situ as well as hydroquinone tests during the progress of reactions. In situ XPS analysis was also used to study the reaction mechanism. To prove the synergistic performance of Co and Cu in the catalyst, its various homologues were synthesized and applied to a model reaction separately, and then their catalytic activities were investigated. Finally, the catalyst could be recovered from the reaction mixture simply, and reused for several cycles with a minimum loss in catalytic activity and performance.
- Allahresani, Ali,Kazemnejadi, Milad,Nasseri, Mohammad Ali,Rezazadeh, Zinat
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p. 10645 - 10660
(2020/09/18)
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- Pd nanoparticles supported on Fe3O4@SiO2-Schiff base as an efficient magnetically recoverable nanocatalyst for Suzuki–Miyaura coupling reaction
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Abstract: In this work, Pd nanoparticles (Pd-NPs) were decorated on modified magnetic nanoparticles (MNPs) and used as an efficient and recyclable catalyst for the Suzuki cross-coupling reaction of aryl halides with phenylboronic acid (PhB(OH)2) in a green solvent. The prepared nanocomposite was characterized by field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, Fourier transforms infrared spectroscopy, X-ray powder diffraction, thermogravimetric analysis/differential thermal analysis, and vibrating sample magnetometry. All analyses confirmed the successful modification of MNPs and immobilization of Pd on modified MNPs. This catalyst exhibited superior catalytic activity and stability in the suzuki cross-coupling reaction of PhB(OH)2 and aryl halide derivatives. This protocol includes some advantages, such as magnetically reusability of the catalyst, mild experimental conditions, green solvent, excellent yields of the product (52–98percent), and short reaction times (4–33?min). The catalyst could be reused for six successive runs without any significant loss of its efficiency. Graphic abstract: [Figure not available: see fulltext.]
- Amirmahani, Najmeh,Mahmoodi, Nosrat O.,Malakootian, Mohammad,Pardakhty, Abbas,Seyedi, Neda
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p. 4595 - 4609
(2020/08/05)
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- Polystyrene-Supported PPh3 in Monolithic Porous Material: Effect of Cross-Linking Degree on Coordination Mode and Catalytic Activity in Pd-Catalyzed C?C Cross-Coupling of Aryl Chlorides
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Hybridization of porous synthetic polymer and sophisticated ligands play an important role in transition-metal catalysis for chemical transformations at laboratory and industrial levels. A monolithic porous polymer, which is a single piece with continuous macropores, is desired for high permeability, fast mass transfer properties, high stability, and easy modification. Herein, we first develop a monolithic porous polystyrene containing three-fold cross-linked PPh3 (M-PS-TPP) for transition-metal catalysis. The monolithic and macroporous structure of M-PS-TPP was fabricated via polymerization-induced phase separation using porogenic solvent. Moreover, the M-PS-TPP was synthesized using different feed ratios of divinylbenzene (DVB) for site-isolation and mono-P-ligating behavior of PPh3. 31P CP/MAS NMR analysis revealed that the different selectivity of M-PS-TPPs was obtained in formation of mono-P-ligation toward PdII. The macroporous properties and controlled mono-P-ligating behavior of M-PS-TPP facilitated the challenging Pd-catalyzed Suzuki-Miyaura cross-coupling reaction of chloroarenes.
- Matsumoto, Hikaru,Hoshino, Yu,Iwai, Tomohiro,Sawamura, Masaya,Miura, Yoshiko
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p. 4034 - 4037
(2020/07/04)
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- Exploration of Fragment Binding Poses Leading to Efficient Discovery of Highly Potent and Orally Effective Inhibitors of FABP4 for Anti-inflammation
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Fatty-acid binding protein 4 (FABP4) is a promising therapeutic target for immunometabolic diseases, while its potential for systemic inflammatory response syndrome treatment has not been explored. Here, a series of 2-(phenylamino)benzoic acids as novel and potent FABP4 inhibitors are rationally designed based on an interesting fragment that adopts multiple binding poses within FABP4. A fusion of these binding poses leads to the design of compound 3 with an ?460-fold improvement in binding affinity compared to the initial fragment. A subsequent structure-aided optimization upon 3 results in a promising lead (17) with the highest binding affinity among all the inhibitors, exerting a significant anti-inflammatory effect in cells and effectively attenuating a systemic inflammatory damage in mice. Our work therefore presents a good example of lead compound discovery derived from the multiple binding poses of a fragment and provides a candidate for development of drugs against inflammation-related diseases.
- Su, Haixia,Zou, Yi,Chen, Guofeng,Dou, Huixia,Xie, Hang,Yuan, Xiaojing,Zhang, Xianglei,Zhang, Naixia,Li, Minjun,Xu, Yechun
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p. 4090 - 4106
(2020/05/20)
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- Copper catalysed Gomberg-Bachmann-Hey reactions of arenediazonium tetrafluoroborates and heteroarenediazonium o-benzenedisulfonimides. Synthetic and mechanistic aspects
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Gomberg-Bachmann-Hey reactions were carried out in the presence of copper as a catalyst and gave rise to biaryls or heterobiaryls in good yields and in mild reaction conditions. A computational study of some key points of the reaction was performed. The results are coherent with the experimental data and confirm some aspects of the mechanism. The reaction free energies for the reduction in benzene by CuI of a set of 40 (hetero)arenediazonium tetrafluoroborates were calculated. Both the experiments and the calculations showed that in the coupling with substituted solvents (toluene, bromobenzene, nitrobenzene and anisole) the binding to the ortho position was always favoured.
- Antenucci, Achille,Barbero, Margherita,Dughera, Stefano,Ghigo, Giovanni
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- Method for synthesizing nitrobiphenyl
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The invention relates to a method for synthesizing nitrobiphenyl. The nitrophenylamine which is low in price and benzene are mixed in a solvent which contains halogenated organic acid, halogenated metal salt and nitrite and react, and then the nitrobiphenyl is obtained by aftertreatment. The raw materials are simple and are easily obtained, and are low in cost. Meanwhile, reaction conditions are mild, aftertreatment is simple, and industrialization is facilitated.
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Paragraph 0046; 0047
(2020/07/24)
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- NITRATION
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The present invention relates to a process for preparing a nitrated compound, comprising the step of reacting a compound (A) comprising at least one substituted or unsubstituted aromatic or heteroaromatic ring, wherein said heteroaromatic ring comprises at least one heteroatom selected from the group consisting of oxygen, sulfur, phosphor, selenium and nitrogen, with a compound of formula (I) wherein Y is selected from the group consisting of hydrogen and nitro.
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Page/Page column 36; 41; 46; 64; 37; 49; 42; 65
(2020/05/28)
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- Tetramethylammonium fluoride tetrahydrate-mediated transition metal-free coupling of aryl iodides with unactivated arenes in air
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Biaryls are important compounds with widespread applications in many fields. Tetramethylammonium fluoride tetrahydrate was found to promote the biaryl coupling of aryl iodides bearing electron-withdrawing substituents with unactivated arenes. The reaction takes place at temperatures between 100 and 150°C and can be applied to a wide range of aromatic and heteroaromatic rings, affording the products in moderate to high yields. The reaction does not require strong bases or expensive additives that are employed in the existing methods and can be conducted in air and moisture without any precautions.
- Nozawa-Kumada, Kanako,Nakamura, Kosuke,Kurosu, Satoshi,Iwakawa, Yuki,Denneval, Charline,Shigeno, Masanori,Kondo, Yoshinori
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p. 1042 - 1045
(2019/10/02)
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- Ni: Vs. Pd in Suzuki-Miyaura sp2-sp2 cross-coupling: A head-to-head study in a comparable precatalyst/ligand system
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The Suzuki-Miyaura reaction is a cornerstone method for sp2-sp2 cross-coupling in industry. There has been a concerted effort to enable the use of Ni catalysis as an alternative to Pd in order to mitigate cost and improve sustainability. Despite significant advances, ligand development for Ni-catalyzed Suzuki-Miyaura cross-coupling remains underdeveloped when compared to Pd and, as a consequence, ligands for Ni-catalyzed processes are typically taken from the Pd arena. In this study we evaluate the effect of using a similar Ni and Pd precatalyst based on a common bidentate ligand (dppf) in a head-to-head format for the most common type of biaryl couplings, establishing the practical implications of direct replacement of Pd with Ni, and identifying the potential origins of these observations in a mechanistic context.
- West, Matthew J.,Watson, Allan J. B.
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supporting information
p. 5055 - 5059
(2019/06/03)
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- Tetradentate amido azo Schiff base Cu(II), Ni(II) and Pd(II) complexes: Synthesis, characterization, spectral properties, and applications to catalysis in C–C coupling and oxidation reaction
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New Schiff base ligands (H2L1 & H2L2) were synthesized by the reaction of salicylaldehyde with (2-((2-aminophenyl)diazenyl)-N-alkylaniline), and were used for the preparation of complexes with Cu(II), Ni(II) and Pd(II) metal ions. The structural features of the synthesized compounds were examined by UV–Vis, IR and 1H NMR spectroscopy. The crystal structures of Schiff base (H2L1) and two metal complexes Cu(L1) and Ni(L2) were determined by single crystal X-ray diffraction. The studies revealed that the synthesized Schiff bases existed as tetradentate (N,N,N,O) ligands and bonded to the metal ions through the donor atoms of the amido nitrogen, azo nitrogen, azomethine nitrogen and phenolic oxygen atoms. The redox property of Cu(L1) and Ni(L1) and emission behavior of ligand H2L1 and complexes Cu(L1) and Ni(L1) were examined. The complex Cu(L1) shows excellent catalytic activity towards oxidation of benzyl alcohol to benzyldehyde (under solvent-free condition) using H2O2 as the oxidant. Complex Pd(L1) acts as highly efficient catalyst in the Suzuki–Miyaura cross-coupling reaction of various aryl halides with phenyl boronic acid to produce the corresponding biaryls with high yields under mild reaction conditions. Both the catalysts Cu(L1) and Pd(L1) were easily recovered by simple chromatographic separation and reused for next catalytic cycle.
- Pratihar, Jahar Lal,Mandal, Paritosh,Lai, Chung Kung,Chattopadhyay, Surajit
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p. 317 - 324
(2019/02/06)
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- Pd embedded N, S co-doped graphene wrapped core-shell magnetic nanospheres: Engineered stable nanocatalyst for Suzuki couplings
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Designed nitrogen and sulfur co-doped graphene wrapped magnetic core-shell supported Pd nanoparticles were synthesized through the following steps. Firstly, Fe3O4 was prepared, coated with silica and then functionalized with amine groups to create a positive charge on the structure for enhancing the interaction of the Fe3O4@SiO2 with graphene oxide. Secondary, the pre-catalyst wrapped with graphene to enhance adsorption of aromatic substrates through π–π stacking. Thirdly, graphene was doped with nitrogen and sulfur to increase the grafting of Pd in hybrid. Finally, Pd NPs were attached on the surface of pre-engineered structure to produce Fe3O4@SiO2@N,S-wG@Pd which exhibited high performance in Suzuki reactions. This superior activity can be indexed to the incorporation of N and S atoms into graphene led to high anchoring and well-dispersion of Pd NPs on the nanocomposite surface offering large amounts of active centers, that strongly increased the interaction between Pd and substrates to decreases Pd leaching.
- Rohani, Sahar,Mohammadi Ziarani, Ghodsi,Badiei, Alireza
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- Palladium/phosphorus-functionalized porous organic polymer with tunable surface wettability for water-mediated Suzuki-Miyaura coupling reaction
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A series of phosphorus-functionalized porous organic polymers supported palladium catalysts with tunable surface wettability were successfully prepared using an easy copolymerization and successive immobilization method. The obtained polymers were carefully characterized by many physicochemical methods. Characterization results suggested that the prepared materials featured hierarchically porous structures, high pore volumes, tunable surface wettability and strong electron-donating ability towards palladium species. We demonstrated the use of these solid catalysts for water-mediated Suzuki-Miyaura coupling reactions. It was found that the surface wettability of the prepared catalysts has an important influence on their catalytic activities. The optimal catalyst, which has excellent amphipathicity and relatively high phosphorus concentration, displayed superior catalytic activity compared to the other catalysts. Under ambient conditions, a variety of aryl chlorides can be efficiently transformed to biaryls in high yields. Moreover, the catalyst could be easily recovered and reused at least six times.
- Lei, Yizhu,Chen, Zaifei,Li, Guangxing
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p. 36600 - 36607
(2019/11/25)
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- Ferrocenyl palladacycles derived from unsymmetrical pincer-type ligands: Evidence of Pd(0) nanoparticle generation during the Suzuki-Miyaura reaction and applications in the direct arylation of thiazoles and isoxazoles
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A new family of ferrocenyl-palladacycle complexes Pd(L1)Cl (Pd1) and Pd(L2)Cl (Pd2) were synthesized and characterized by UV-visible, IR, ESI-MS, and NMR spectral studies. The molecular structures of Pd1 and Pd2 were determined by X-ray crystallographic studies. Palladacycle catalyzed Suzuki-Miyaura cross-coupling reactions were investigated utilizing the derivatives of phenylboronic acids and substituted chlorobenzenes. Mechanistic investigation authenticated the generation of Pd(0) nanoparticles during the catalytic cycle and the nanoparticles were characterized by XPS, SEM and TEM analysis. Direct C-H arylation of thiazole and isoxazole derivatives employing these ferrocenyl-palladacycle complexes was examined. The reaction model for the arylation reaction implicating the in situ generation of Pd(0) nanoparticles was proposed.
- Maji, Ankur,Singh, Anshu,Mohanty, Aurobinda,Maji, Pradip K.,Ghosh, Kaushik
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supporting information
p. 17083 - 17096
(2019/11/26)
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- Biological and catalytic potential of sustainable low and high valent metal-Schiff base sulfonate salicylidene pincer complexes
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ONO-Pincer Schiff base salicylidene (HSaln ligand) complexes with VO2+, UO22+, MoO22+ and Mn2+ ions (MSaln complexes = VOSaln, UO2Saln, MoO2Saln and MnSaln, respectively) were synthesized and fully characterized by different physico-chemical tools. The VOSaln complex was further treated with 1,10-phenanthroline which afforded a new VO-complex (VOSaln-Ph). All complexes and their ligands, as eco-friendly reagents, were explored for their biological potential as antibacterial and antifungal agents. Reactivity of MSaln complexes against the tested pathogen strains exhibited a remarkable inhibitory effect compared to the coordinated ligand (HSaln) and applicable standard drugs. Moreover, the MSaln complex-DNA interaction was investigated by ultraviolet-visible spectroscopy, viscosity and gel electrophoresis techniques affording binding strengths in the order: UO2Saln > MnSaln > MoO2Saln > VOSaln-Ph > VOSaln. Additionally, the biological potential of the investigated compounds was further explored by molecular docking to illustrate the nature of the drug-DNA interactions. All MSaln complexes show respectable anti-proliferative potential as anticancer agents against selected human carcinoma cell lines. Aside from the biological activities these complexes (MSaln complexes) were also investigated for catalytic efficiency in the Suzuki-Miyaura cross-coupling system of phenylboronic acid with 2-bromopyridine in water, sustainably. The results indicated that the MnSaln catalyst performed well with high yield. The catalytic potential of MnSaln was compared in water, water-ionic liquid mixtures and ionic liquids.
- Adam, Mohamed Shaker S.,El-Hady, Omar M.,Ullah, Farman
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p. 34311 - 34329
(2019/11/11)
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- A Graphene Oxide Nanosheet Supported NHC-Palladium Complex as a Highly Efficient and Recyclable Suzuki Coupling Catalyst
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A practical heterogeneous catalyst was prepared by anchoring a triazine-tethered N-heterocyclic carbene (NHC)-palladium complex on the surface of graphene oxide (GO) nanosheets. The immobilized complex was characterized by X-ray photoelectron spectroscopy, field-emission transmission electron microscopy, energy-dispersive X-ray spectroscopy, and surface area analysis. It proved to be a highly active and durable heterogeneous catalyst for Suzuki coupling reactions. At room temperature, the use of this catalyst enabled the preparation of various biaryls and heterobiaryls in short reaction times. The catalytic system could be recycled at least 10 times with almost consistent activity. The results reveal that the stable palladium complex is strongly anchored on the surface of GO nanosheets. Interestingly, an open planar network of the GO nanosheet support plays a role during the catalytic process in enhancing the catalytic activity.
- Qian, Yingjie,So, Jaeil,Jung, Sang-Yung,Hwang, Sosan,Jin, Myung-Jong,Shim, Sang Eun
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p. 2287 - 2292
(2019/05/28)
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- Perylenequinonoid-catalyzed photoredox activation for the direct arylation of (het)arenes with sunlight
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Naturally occurring perylenequinonoid pigments (PQPs) have attracted considerable attention owing to their excellent properties of photosensitization. They have been widely investigated as an aspect of photophysics and photobiology. However, their applications in photocatalysis are yet to be explored. We report here that sunlight along with 1 mol% cercosporin, which is one of the perylenequinonoid pigments, catalyzes the direct C-H bond arylation of (het)arenes by a photoredox process with good regioselectivity and broad functional group compatibility. Furthermore, a gram-scale reaction with great conversions of substrates was achieved even by a cercosporin-containing supernatant without organic solvent extraction and purification after liquid fermentation. Thus we set up a bridge between microbial fermentation and organic photocatalysis for chemical reactions in a sustainable, environmentally friendly manner.
- Zhang, Shiwei,Tang, Zhaocheng,Bao, Wenhao,Li, Jia,Guo, Baodang,Huang, Shuping,Zhang, Yan,Rao, Yijian
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supporting information
p. 4364 - 4369
(2019/05/10)
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- Ferrocene-Labeled Carbon-Encapsulated Iron Nanoparticles: The First Magnetic Nanocatalysts for C-H Arylation toward 1,1′-Biphenyl Formation
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The first magnetic nanocatalysts for C-H arylation toward 1,1′-biphenyl formation are described. The nanocatalysts are based on conjugates of ferrocene and carbon-encapsulated iron nanoparticles. The highest catalytic activity was found for ferrocene conjugated to carbon-encapsulated iron nanoparticles via the N-methylpyrrolidine moiety. In the presence of the nanocatalyst, various 1,1′-biphenyls can be obtained in high yields (84-90%). The effect of substitution of the aniline's phenyl ring on the reaction yield is also included in this work. The nanocatalyst can be easily separated from the reaction mixture and can be reused in up to four reaction cycles without any loss of its high catalytic activity. Our work sheds light on a potential application of functionalized carbon-encapsulated iron nanoparticles in modern industrial organic processes toward more economical manufacturing of organic compounds.
- Kasprzak, Artur,Bystrzejewski, Michal,Poplawska, Magdalena
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supporting information
p. 409 - 415
(2019/03/11)
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- Base-free Pd-MOF catalyzed the Suzuki-Miyaura cross-coupling reaction of arenediazonium tetrafluoroborate salts with arylboronic acids
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A convenient and environmental benign synthesis of biaryls has been demonstrated by a straightforward reaction catalyzed by the palladium-containing metal-organic framework (Pd-MOF) [Pd (2-pymo)2]n (2-pymo = 2-pyrimidinolate). A series of functionalized biaryl derivatives have been synthesized in good to excellent yields by the Suzuki-miyaura cross-couplings of sustainable arenediazonium salts with a variety of arylboronic acids and the reactions were catalyzed by the Pd-MOF using methanol as a benign solvent. Those base- and additive-free catalytic reactions proceeded smoothly under non-anhydrous and non-degassed condition. Such transformation avoided high reaction temperature, tolerated many functional groups and presented a wide substrate scope. The catalyst could be recovered by filtration and reused for four successive cycles before collapse of the MOF structure.
- Liu, Yangyang,Wang, Jie,Li, Tang,Zhao, Zesheng,Pang, Wan
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- Atom-efficient Pd-catalyzed cross-couplings of chloroarenes with triarylbismuth reagents
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Various Pd-catalyzed protocols have been developed for the atom-efficient cross-coupling of chloroarenes with triarylbismuth reagents. Using the developed protocols, an efficient synthesis of unsymmetrical biaryls in good to excellent yields was achieved by employing electron-deficient chloroarenes and a range of triarylbismuth reagents.
- Rao, Maddali L.N.,Meka, Suresh
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supporting information
(2019/07/30)
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- Preparation method of substituted nitrobenzene compound
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The invention discloses a preparation method of a substituted nitrobenzene compound. The method comprises the following steps: carrying out a decarboxylation reaction as shown below on a compound II under the action of alkali in a solvent at the temperature of 150 to 250 DEG C to obtain a compound I; the alkali is one or more of carbonates and bicarbonates of alkali metals. Compared with some metal-catalyzed decarboxylation methods, the preparation method of the substituted nitrobenzene compound has the advantages of simple operation, low production cost, convenient post-treatment and high yield, and more application values in industrial production.
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Paragraph 0092-0095
(2019/03/29)
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- Sterically hindered N-heterocyclic carbene/palladium(ii) catalyzed Suzuki-Miyaura coupling of nitrobenzenes
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Palladium-catalyzed denitrative Suzuki coupling of nitroarenes using 2-aryl-5-(2,4,6-triisopropylphenyl)-2,3-imidazolylidene[1,5-a]pyridines as the ligands is described. The key to success is the use of the NHC ligands which show strong donating ability and suitable steric hindrance allowing the successful oxidative addition of Ar-NO2 bonds. Both aromatic and aliphatic boronic acids are tolerated, and a variety of biphenyls and alkylarenes were obtained in good to excellent yields.
- Chen, Kai,Chen, Wei,Yi, Xiaofei,Chen, Wanzhi,Liu, Miaochang,Wu, Huayue
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supporting information
p. 9287 - 9290
(2019/08/08)
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- Method for synthesizing aromatic compound by coupling palladium/imidazole salt with nitroaromatic hydrocarbon and boric acid compound (by machine translation)
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The invention discloses a method, for coupling a palladium/imidazole salt with a nitroaromatic hydrocarbon and a boric acid compound to synthesize an aromatic compound. The method comprises: in organic solvent, taking nitroaromatic hydrocarbon and boric acid compound as substrate, palladium/imidazole salt as a catalyst, carrying out coupling reaction under the action of alkali, and carrying out post-treatment to obtain the aromatic compound. The method is simple, easy to store, low in price, relatively low in ligand consumption, high in product yield, good in substrate applicability, and suitable for alkyl boronic acid. The process of the invention can be used to synthesize a series of aromatic compounds, for example. The compound has wide application value in the fields of pesticides, medicines, materials and the like. (by machine translation)
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Paragraph 0099-0103
(2019/10/01)
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- Nickel-catalyzed cross-coupling of: O, N -chelated diarylborinates with aryl chlorides and mesylates
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A practical nickel catalyst system consisting of readily available components, trans-NiCl(Ph)(PPh3)2/[Iprmim]I/K3PO4·3H2O in toluene, has been developed for efficient cross-coupling of 3-dimethylaminopropyl diarylborinates with aryl chlorides and mesylates. A small amount of water has been found to be crucial in achieving high efficiency in the system. The nickel catalyst system displayed remarkably higher activities to aryl chlorides and mesylates than the corresponding tosylates in cross-coupling with not only diarylborinates but also diarylborinic acids, arylboronic acids, anhydrides and trifluoroborates as indicated in control experiments. A variety of electronically various biaryls could be obtained in excellent yields by using 3-5 mol% loading of the nickel catalyst while sterically hindered biaryls were obtained in comparably lower yields.
- Ren, Chao,Zeng, Jingshu,Zou, Gang
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supporting information
p. 1589 - 1596
(2019/01/23)
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- Enhancement of Suzuki–Miyaura coupling reaction by photocatalytic palladium nanoparticles anchored to TiO2 under visible light irradiation
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Plasmonic property and catalytic performance of Pd anchored to TiO2 for Suzuki?Miyaura coupling (SMC) reactions are reported. Different from previous reports, this semiconductor with band gap ≥3 eV can afford C–C bond formation for SMC. Nano Pd/TiO2 was successfully synthesized through a photodeposition method under sunlight. The size of Pd nanoparticles onto the surface of TiO2 led to enhancement of localized surface plasmon resonance. This visible-light-harvesting heterogeneous photocatalyst sufficiently promoted substrates toward coupling reaction products at ambient temperature in aqueous media. Photo-generated electron-hole pairs under visible light irradiation, are the key components of activation of the substrates.
- Koohgard, Mehdi,Hosseini-Sarvari, Mona
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- Ligand-Free Bioinspired Suzuki–Miyaura Coupling Reactions using Aryltrifluoroborates as Effective Partners in Deep Eutectic Solvents
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Pd-catalyzed Suzuki–Miyaura cross-coupling between (hetero)aryl halides (Cl, Br, I) and versatile, moisture-stable mono- and bifunctional potassium aryltrifluoroborates proceeded efficiently and chemoselectively in air and under generally mild conditions; a catalyst loading as low as 1 mol % combined with Na2CO3 as a base in choline chloride/glycerol (1:2) deep eutectic solvent (DES) was used as a sustainable and environmentally responsible medium. The catalyst, base, and DES were easily and successfully recycled up to six times with an E-factor as low as 8.74. Valuable biaryls and terphenyl derivatives were furnished in yields of up to 98 %; over 50 reactions were compared and discussed. The methodology was applied for the synthesis of the nonsteroidal anti-inflammatory drugs Felbinac and Diflunisal.
- Dilauro, Giuseppe,García, Sergio Mata,Tagarelli, Donato,Vitale, Paola,Perna, Filippo M.,Capriati, Vito
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p. 3495 - 3501
(2018/09/21)
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- A tetranuclear CuII2DyIII2 coordination cluster as a Suzuki (C-C) coupling reaction promoter
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The air-stable tetranuclear coordination cluster [CuII2DyIII2L4(NO3)2(CH3CN)2]·2(CH3CN), which can be obtained in high yield, promotes the Suzuki coupling reaction of phenylboronic acid with substituted aryl halides under environmentally benign conditions.
- Kumar, Prashant,Griffiths, Kieran,Anson, Christopher E.,Powell, Annie K.,Kostakis, George E.
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supporting information
p. 17202 - 17205
(2019/01/03)
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- Method for preparing bi-arene from aryl diazo salts and aryl sulfonylhydrazide
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The invention discloses a method for preparing bi-arene from aryl diazo salts and aryl sulfonylhydrazide. The method comprises the following steps of performing denitrification coupling reaction on aryl diazo salts and aryl sulfonylhydrazide in an organic solvent under the effects of palladium catalysts, ligands and additives; after the reaction is completed, performing post-treatment to obtain the bi-arene. The method provided by the invention has the advantages that the substrate price is low; the property is stable; the operation is convenient; meanwhile, the reaction yield is high; the substrate general applicability is high.
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Paragraph 0041; 0042; 0043
(2018/10/19)
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- Pd immobilized on polyamide based on melamine and terephalic acid as an efficient and recyclable catalyst for Suzuki-Miyaura coupling reaction
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A simple synthetic strategy of polyamide was described from melamine and terephalic acid via one-step polycondensation. PdCl2 was then immobilized on the polyamide (denoted as Pd/MPA). Melamine and terephalic acid not only acted as monomers but also provided the ligand sites to help the polyamide to coordinate with Pd(II). The Pd/MPA catalyst was characterized by FT-IR, TGA, SEM, TEM, XPS, N2 adsorption-desorption and atomic absorption spectroscopy. The catalyst was used in Suzuki-Miyaura coupling reaction of various aryl halides, including less reactive chlorobenzene and benzyl chloride, to give the coupling products in moderate to excellent yields. High turnover frequencies (TOF) up to 29400 h-1 can be also obtained. In addition, it behaved truly as a heterogeneous catalyst with high reusability after being recycled 6 times and palladium leaching was negligible during the process. This work provides a practical polyamide support to develop heterogeneous palladium catalysts with simple synthetic procedure and low cost.
- Chen, Jian,Zhang, Ju,Sun, Weiting,Song, Kunpeng,Zhu, Dajian,Li, Tao
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- Mild-Base-Promoted Arylation of (Hetero)Arenes with Anilines
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Transition metal-free radical arylation of heteroarenes is achieved at room temperature by simply adding aqueous sodium carbonate to a solution of the corresponding heteroarene and arenediazonium salt, which can even be formed in situ. Such an easy, inexpensive and mild methodology has been optimized and applied to the expeditious modification of interesting molecular cores like naphthylimide or bisthienylcyclopentenes.
- Monzón, Diego M.,Santos, Tanausú,Pinacho-Crisóstomo,Martín, Víctor S.,Carrillo, Romen
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supporting information
p. 325 - 333
(2018/01/15)
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- Method for nitrating aromatic compound by using nitrate under the action of auxiliary agent
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The invention discloses a method for nitrating an aromatic compound by using a nitrate under the action of an auxiliary agent, and provides an aromatic nitro compound preparation method, which comprises: in the presence of an external action and an auxiliary agent, carrying out a nitrating reaction on an aromatic compound and a metal nitrate or a hydrate thereof to obtain the aromatic nitro compound, wherein the external action can cause the physical and/or chemical property change of a substance, the auxiliary agent is a substance having water absorbing ability, the external action can be mechanical force or heating, and the mechanical force can be any one selected from compression, shearing, impacting, friction, stretching, bending and vibration. According to the present invention, the method does not require any solvents so as to avoid the generation of the waste liquid; the acidic substance is not used, such that the treatment is simple after the reaction is completed, and the equipment is not damaged; the added auxiliary agent can be theoretically recycled; and the method has extremely high conversion rate and extremely high selectivity, and can be used for the nitration of conventional aromatic compounds.
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Paragraph 0053-0066
(2018/09/11)
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- Mechanical force under the action of the nitration of aromatic compounds of nitrate method (by machine translation)
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The invention discloses a mechanical force under the action of the nitration of aromatic compounds of nitrate method. The invention provides a method for preparing aromatic nitro compounds, comprising the following steps: under the action of mechanical force, aromatic compound with a metal nitrate or its hydrate by the nitration reaction, to obtain the aromatic nitro compound; the mechanical fastener is machinery offers can cause material physical and/or chemical nature of the change of the external force. The mechanical force can be compression, shear, impact, friction, tensile, bending and vibration of any kind. The invention has the following advantages: without the use of any solvent, thereby avoiding the waste liquid produced; and without the use of the acidic substance, the reaction is complete after treatment is simple, without any damage to the apparatus; a very high conversion and selectivity, can be applied to the nitration of conventional aromatic compound. (by machine translation)
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Paragraph 0054; 0055; 0058; 0059
(2018/09/11)
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- Gold(i)-catalyzed cross-coupling reactions of aryldiazonium salts with organostannanes
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Gold(i)-catalyzed cross-coupling reactions of aryldiazonium salts with organostannanes are described. This redox neutral strategy offers an efficient approach to diverse biaryls, vinyl arenes and arylacetylenes. Monitoring the reaction with NMR and ESI-MS provided strong evidence for the in situ formation of Ph3PAuIR (R = aryl, vinyl and alkynyl) species which is crucial for the activation of aryldiazonium salts.
- Akram, Manjur O.,Shinde, Popat S.,Chintawar, Chetan C.,Patil, Nitin T.
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p. 2865 - 2869
(2018/05/03)
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- Desulfinative and denitrogenative palladium-catalyzed cross-coupling of arylsulfonyl hydrazides with aryl diazonium salts
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Palladium-catalyzed cross-coupling of arylsulfonyl hydrazides with aryl diazonium salts to provide biaryl products under relatively mild conditions is established. This reaction proceeded smoothly with tetrabutylammonium iodide and gave the corresponding
- Shang, Yonghui
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- Modular Functionalization of Arenes in a Triply Selective Sequence: Rapid C(sp2) and C(sp3) Coupling of C?Br, C?OTf, and C?Cl Bonds Enabled by a Single Palladium(I) Dimer
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Full control over multiple competing coupling sites would enable straightforward access to densely functionalized compound libraries. Historically, the site selection in Pd0-catalyzed functionalizations of poly(pseudo)halogenated arenes has been unpredictable, being dependent on the employed catalyst, the reaction conditions, and the substrate itself. Building on our previous report of C?Br-selective functionalization in the presence of C?OTf and C?Cl bonds, we herein complete the sequence and demonstrate the first general arylations and alkylations of C?OTf bonds (in I dimer. This allowed the realization of the first general and triply selective sequential C?C coupling (in 2D and 3D space) of C?Br followed by C?OTf and then C?Cl bonds.
- Keaveney, Sinead T.,Kundu, Gourab,Schoenebeck, Franziska
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supporting information
p. 12573 - 12577
(2018/09/18)
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- Direct Aryl-Aryl Coupling without Pre-Functionalization Enabled by Excessive Oxidation of Two-Electron Ag(I)/Ag(III) Catalyst
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Reported herein is a catalytic platform for formation of unsymmetrical biaryls by the coupling between inert Csp2?CH3 and Csp2?H via a tandem catalytic strategy. The platform utilizes traditional AgNO3 catalyst and excess amount of K2S2O8 oxidant. The excessive oxidant present converts the traditional one-electron Ag(I)/Ag(II) chemistry to two-electron Ag(I)/Ag(III) one, enabling one-pot synthesis of aryl-aryl scaffolds by using unactivated cheap commodity chemicals. (Figure presented.).
- Singh, Ajay K.,Kim, Min-Gyu,Lee, Hyune-Jea,Singh, Rakhi,Cho, Seung Hwan,Kim, Dong-Pyo
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supporting information
p. 2032 - 2042
(2018/04/11)
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