92-66-0Relevant academic research and scientific papers
Acceleration of Suzuki coupling reactions by abundant and non-toxic salt particles
Zhang, Binbin,Song, Jinliang,Liu, Huizhen,Shi, Jinghua,Ma, Jun,Fan, Honglei,Wang, Weitao,Zhang, Peng,Han, Buxing
, p. 1198 - 1201 (2014)
Enhancement of reaction efficiency using non-toxic, abundant, and cheap additives is an interesting topic in green chemistry. In this paper, we report the first work to study the effect of salt particles on organic reactions in different solvents, in which the salts were not soluble, and it was discovered that NaCl, KCl, Na2SO4 and K2SO4 particles could considerably accelerate Suzuki coupling reactions catalyzed by the Pd nanocatalysts. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR) studies indicated that there exist strong interactions between the salts and the catalyst (Pd) and between the salts and the reactants, which are important reasons for the synergistic effect of the catalyst and the salts. The application of salt particles suspended in organic reaction systems may become a useful strategy to develop new and green reaction routes.
Transfer of heterocyclic carbene ligands from chromium to gold, palladium and platinum
Kessler, Florian,Szesni, Normen,Maa?, Chaya,Hohberger, Christiane,Weibert, Bernhard,Fischer, Helmut
, p. 3005 - 3018 (2007)
The reaction of pentacarbonyl(pyrazolin-3-ylidene)chromium complexes, {A figure is presented} (2a-c) (R = Ph (a), C6H4NMe2-4 (b); (C5H4)FeCp (c)), with [AuCl(SMe2)], H[AuCl4], [PdCl2(NCPh)2] and [PtCl2(NCPh)2] gives, by transfer of the heterocyclic carbene ligand, new chloro pyrazolin-3-ylidene complexes of gold(I) and gold(III), dichloro bis(pyrazolin-3-ylidene) palladium and dichloro bis(pyrazolin-3-ylidene) platinum in high yield. The chloride ligand in {A figure is presented} (Fc = (C5H4)FeCp) is readily displaced by trifluoroacetate. The analogous substitution of iodide for the chloride ligands in {A figure is presented} (M = Pd, Pt) give the corresponding diiodo complexes although in a much slower reaction. In contrast, the reaction of silver trifluoroacetate with {A figure is presented} affords a binuclear Pd-Ag complex containing two pyrazolin-3-ylidene and three trifluoroacetate ligands two of whom occupy bridging positions between Pd and Ag. The reactions of the pyrazolidin-3-ylidene complex {A figure is presented} (R = C6H4NMe2-4) with [AuCl(SMe2)] and [PdCl2(NCPh)2] yield chloro pyrazolidin-3-ylidene gold and dichloro bis(pyrazolidin-3-ylidene) palladium complexes. The related dichloro bis(tetrahydropyrimidin-4-ylidene) palladium complex is formed in the reaction of {A figure is presented} with the palladium complex [PdCl2(NCPh)2]. The solid-state structures of several of these heterocyclic carbene complexes including the structure of the binuclear Pd-Ag complex are established by X-ray structure analyses.
Supramolecular Nanotubules as a Catalytic Regulator for Palladium Cations: Applications in Selective Catalysis
Wu, Shanshan,Li, Yongguang,Xie, Siying,Ma, Cong,Lim, Joonwon,Zhao, Jiong,Kim, Dae Seok,Yang, Minyong,Yoon, Doong Ki,Lee, Myongsoo,Kim, Sang Ouk,Huang, Zhegang
, p. 11511 - 11514 (2017)
Despite the recent development of highly efficient and stable metal catalysts, conferral of regulatory characteristics to the catalytic reaction in heterogeneous systems remains a challenge. Novel supramolecular nanotubules were prepared by alternative stacking from trimeric macrocycles, which was found to be able to coordinate with Pd cations. The Pd complexes exhibited a high catalytic performance for C?C coupling reaction. Notably, the tubular catalyst was observed to be controlled by supramolecular reversible assembly and showed superior heterogeneous catalytic activity, which was maintained for a number of cycles or reuse under an aerobic environment. Furthermore, the supramolecular catalyst showed unprecedented selectivity for the multifunctional coupling reaction and was able to serve as a new constructor of asymmetrical compounds.
Sterically enhanced 2-iminopyridylpalladium chlorides as recyclable ppm-palladium catalyst for Suzuki–Miyaura coupling in aqueous solution
Lin, Wenhua,Zhang, Liping,Ma, Yanping,Liang, Tongling,Sun, Wen-Hua
, (2021/10/20)
Sterically hindered 2-iminopyridine derivatives and their palladium chlorides complexes are designed and prepared, which efficiently promote the Suzuki–Miyaura coupling (SMC) reaction in aqueous solution. Besides the good to excellent yields and broad substrate scope, these catalysts can be reused for at least four new batches of the substrates. Spontaneous separation of coupling products in the aqueous reaction medium is the additional striking feature of this catalytic process. Furthermore, catalytic performance of palladium complexes bearing the azo-bridged phenyl groups was greatly influenced by the UV irradiation due to the cis/trans photoisomerization of azo unit of the catalysts. In conclusion, titled palladium complexes provide a green, sustainable, cost-effective, and convenient process to synthesize SMC products at multi-gram-scale reaction.
Organocatalytic synthesis of (Het)biaryl scaffoldsviaphotoinduced intra/intermolecular C(sp2)-H arylation by 2-pyridone derivatives
Das, Tapas Kumar,Kundu, Mrinalkanti,Mondal, Biswajit,Ghosh, Prasanjit,Das, Sajal
, p. 208 - 218 (2021/12/29)
A uniqueN,O-bidentate ligand 6-oxo-1,6-dihydro-pyridone-2-carboxylic acid dimethylamide (L1) catalyzed direct C(sp2)-H (intra/intermolecular) arylation of unactivated arenes has been developed to expedite access to (Het)biaryl scaffolds under UV-irradiation at room temperature. The protocol tolerated diverse functional groups and substitution patterns, affording the target products in moderate to excellent yields. Mechanistic investigations were also carried out to better understand the reaction pathway. Furthermore, the synthetic applicability of this unified approach has been showcasedviathe construction of biologically relevant 4-quinolone, tricyclic lactam and sultam derivatives.
Recycling Oryza sativa wastes into poly-imidazolium acetic acid-tagged nanocellulose Schiff base supported Pd nanoparticles for applications in cross-coupling reactions
Elshaarawy, Reda F. M.,Yahya, Rana
, (2021/12/22)
A green and sustainable heterogeneous nanocatalyst for the Suzuki reaction was fabricated by refining rice straw to ionic nanocellulose Schiff base (NCESB) which was employed for bio-reduction of Pd(II) into Pd nanoparticles (Pd NPs) and immobilization of these NPs to fabricate the desired nanocatalyst (NCESB@Pd). The TEM image revealed well-dispersed PdNPs with sizes of 5–23 nm. The new nanocatalyst displayed amazing activity in catalyzing coupling reactions of a wide range of halobenzenes with phenylboronic acid at 50 °C (reaction time 15–60 min) and even at room temperature (reaction time 120 min). The NCESB@Pd nanocatalyst exhibited excellent recyclability (up to five catalytic runs) without a significant loss of its activity or identity. Therefore, the new ionic nanocatalyst may open a new window for a novel generation of ionic low-cost green and highly effective nanocatalysts for organic transformation reactions.
A Photoreactive Iron(II) Complex Luminophore
Argüello Cordero, Miguel A.,Berkefeld, Andreas,Leis, Wolfgang,Lochbrunner, Stefan,Schubert, Hartmut
supporting information, p. 1169 - 1173 (2022/02/05)
Controlling the order and lifetimes of electronically excited states is essential to effective light-to-potential energy conversion by molecular chromophores. This work reports a luminescent and photoreactive iron(II) complex, the first performant group homologue of prototypical sensitizers of ruthenium. Double cyclometalation of a phenylphenanthroline framework at iron(II) favors the population of a triplet metal-to-ligand charge transfer (3MLCT) state as the lowest energy excited state. Near-infrared (NIR) luminescence exhibits a monoexponential decay with τ = 2.4 ns in the solid state and 1 ns in liquid phase. Lifetimes of 14 ns at 77 K are in line with a narrowing of the NIR emission band at λem,max = 1170-1230 nm. Featuring a 3MLCT excited-state redox potential of -2 V vs the ferrocene/ferrocenium couple, the use of the Fe(II) chromophore as a sensitizer for light-driven synthesis is exemplified by the radical cross-coupling of 4-chlorobromobenzene and benzene.
Biaryl Coupling of Aryldiazonium Salts and Arylboronic Acids Catalysed by Gold
Medina-Mercado, Ignacio,Porcel, Susana
, (2022/03/15)
A gold-catalysed coupling of aryldiazonium salts with arylboronic acids is described. The reactions proceed in satisfactory yields under irradiation with blue LEDs in the presence of KF and a catalytic amount of ascorbic acid. Notably, 4-nitrobenzendiazonium tetrafluoroborate is sufficiently reactive to undergo the coupling with a variety of arylboronic acids in the absence of aryl radical initiators. The coupling is applicable for electron-donating and electron-withdrawing groups present at the para, ortho, and meta positions of both substrates.
Highly Active Fe3O4@SBA-15@NHC-Pd Catalyst for Suzuki–Miyaura Cross-Coupling Reaction
?zdemir, ?smail,Akko?, Mitat,Alt?n, Serdar,Bu?day, Nesrin,Ya?ar, Sedat
, (2021/08/03)
A novel Pd-NHC functionalized magnetic Fe3O4@SBA-15@NHC-Pd was synthesized and used as an efficient heterogeneous catalyst in the Suzuki–Miyaura C–C bond formation reactions. The Fe3O4@SBA-15@NHC-Pd characterized by X-Ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared (FTIR) spectroscopy, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy?(TEM), Energy Dispersive X-ray analysis (EDX), Thermogravimetric Analysis (TGA), Differential Thermal Analysis (DTA). The Inductively Coupled Plasma-Optical emission spectroscopy (ICP-OES)?analysis was used to determine the exact amount of Pd (0.33?wt%) in Fe3O4@SBA-15@NHC-Pd. The TEM images of the catalyst showed the existence of palladium nanoparticles immobilized in the catalyst's structure, while no reducing agent was used. The NHC moieties in the catalyst structure could be stabilize Pd(0) nanoparticles prevents agglomeration. The magnetic catalyst was effectively used in the Suzuki–Miyaura cross-coupling reaction of substituted phenylboronic acid derivatives with (hetero)aryl bromides in the presence of a K2CO3 at room temperature in aqueous media and magnetic catalyst could be simply extracted from the reaction mixture by an external magnet. Different aryl bromides were converted to coupled-products in excellent yields with spectacular TOFs values (up to 1,960,339?h?1); in the presence of 1?mg of Fe3O4@SBA-15@NHC-Pd catalyst (contains 3.1 × 10–6?mol% Pd) at room temperature in aqueous media. After reusability experiments, it is found that this catalyst was effectively used up to ten times in the reaction with almost consistent catalytic efficiency. A decrease in the activity of the 10th reused catalyst was found as 9%. Graphic Abstract: [Figure not available: see fulltext.]
Magnetite@MCM-41 nanoparticles as support material for Pd-N-heterocyclic carbene complex: A magnetically separable catalyst for Suzuki–Miyaura reaction
Akko?, Mitat,Bu?day, Nesrin,Alt?n, Serdar,Ya?ar, Sedat
, (2021/03/22)
The Magnetite@MCM-41@NHC@Pd catalyst was obtained with Pd metal bound to the NHC ligand anchored to the surface of Fe3O4@MCM-41. It was characterized by Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy disperse X-ray analysis (EDX), thermogravimetric analysis (TGA), differential thermal analysis (DTA), and scanning electron microscopy (SEM). The amount of Pd in the Magnetite@MCM-41@NHC@Pd was measure by inductively coupled plasma–optical emission spectroscopy (ICP-OES) analysis. The catalytic activity of Magnetite@MCM-41@NHC@Pd heterogeneous catalyst done on Suzuki–Miyaura reactions of aryl halides with different substituted arylboronic acid derivatives. All coupling reactions afforded excellent yields and up to 408404 Turnover Frequency (TOF) h?1 in the presence of 2 mg of Magnetite@MCM-41@NHC@Pd catalyst (0.0564 mmol g?1, 0.01127 mmol% Pd) at room temperature in 2-propanol/H2O (1:2). Moreover, Magnetite@MCM-41@NHC@Pd catalyst was recover by applying the magnet and reused for another reaction. The catalyst showed excellent structural and chemical stability and reused ten times without a substantial loss in its catalytic performance.
