- Suzuki-Miyaura Cross-Coupling Using Plasmonic Pd-Decorated Au Nanorods as Catalyst: A Study on the Contribution of Laser Illumination
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The interaction between plasmonic metal catalysts and visible light can be exploited to increase their catalytic activity. This activity increase results from the generation of hot charge carriers or hot surfaces, or a combination of both. We have studied the light-induced Suzuki-Miyaura cross-coupling reaction of bromobenzene and m-tolylboronic acid using Pd-decorated Au nanorods as plasmonic catalyst in order to assess which physical effect dominates. Comparative experiments under laser illumination and in dark were performed, demonstrating that under the experimental conditions applied in our study the catalytic activity achieved upon illumination is dominantly based on the conversion of light to heat by the plasmonic catalyst. Pd leached from the catalyst also plays a significant role in the reaction mechanism.
- Verkaaik, Mattheus,Grote, Roos,Meulendijks, Nicole,Sastre, Francesc,Weckhuysen, Bert M.,Buskens, Pascal
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- Novel imidazolium and imidazolinium salts containing the 9-nickelafluorenyl anion - Synthesis, structures and reactivity
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Investigation of the properties of carbene complexes is one of the most important fields of modern coordination chemistry. In this paper, we propose the convenient synthesis of NHC-nickel compounds. The 9-nickelafluorenyllithium complex reacts with imidazolium or imidazolinium salts to afford 9-nickelafluorenyl-NHC salts via ionic metathesis with very good yields (66-92%). These compounds can be isomerised at elevated temperatures to give Ni-NHC complexes with excellent yields (88-91%), probably via nickel mediated hydrogen transfer to the biphenyl moiety. In this reaction, the nickelacyclic ring itself serves as a base in the deprotonation of the carbene precursor. DFT calculations show the thermodynamic instability of the synthesized salts, with Gibbs free energy differences for 1 of -84 kJ mol-1 at 298 K and -167 kJ mol-1 at 374 K. The obtained salts and carbene complexes are relatively air and moisture stable in the solid state.
- Buchalski, Piotr,Pacholski, Roman,Chodkiewicz, Krzysztof,Buchowicz, W?odzimierz,Suwińska, Kinga,Shkurenko, Aleksander
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- A novel fluorous palladium catalyst for Suzuki reaction in fluorous media
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Palladium(II) perfluorooctanesulfonate [Pd(OSO2Rf8)2] catalyses the highly efficient Suzuki reaction in the presence of a catalytic amount of perfluoroalkylated-pyridine as a ligand in a fluorous biphase system (FBS). The fluorous phase containing the active palladium species is easily separated and can be reused several times without a significant loss of catalytic activity.
- Shen, Ming-Gui,Cai, Chun,Yi, Wen-Bin
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- Nickel(II) complexes of bidentate N-heterocyclic carbene/phosphine ligands: Efficient catalysts for suzuki coupling of aryl chlorides
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Nickel(II) complexes of bidentate N-heterocyclic carbene (NHC)/phosphane ligand L were prepared and structurally characterized. Unlike palladium, which forms [PdCl2(L)], the stable nickel product isolated is the ionic [Ni(L)2]Cl2. These NiII complexes are highly robust in air. Among different N-substituents on the ligand framework, the nickel complex of ligand L bearing N-1-naphthylmethyl groups (2 a) is a highly effective catalyst for Suzuki cross-coupling between phenylboronic acid and a range of aryl halides, including unreactive aryl chlorides. The activities of 2a are largely superior to those of other reported nickel NHC complexes and their palladium counterparts. Unlike the previously reported [NiCl2(dppe)] (dppe = 1,2-bis(diphenylphosphino)ethane), 2a can effectively catalyze the cross-coupling reaction without the need for a catalytic amount of PPh 3, and this suggests that the PPh2 functionality of hybrid NHC ligand L can partially take on the role of free PPh3. However, for unreactive aryl chlorides at low catalyst loading, the presence of PPh 3, accelerates the reaction.
- Lee, Chun-Chin,Ke, Wei-Chi,Chan, Kai-Ting,Lai, Chun-Liang,Hu, Ching-Han,Lee, Hon Man
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- Magnetic Mesoporous Silica Nanocomposite Functionalized with Palladium Schiff Base Complex: Synthesis, Characterization, Catalytic Efficacy in the Suzuki–Miyaura Reaction and α-Amylase Immobilization
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Abstract: Magnetic mesoporous silica nanocomposite, Fe3O4-MCM-41, was functionalized with N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (AEAPS) and then condensed with 5,5′-methylene bis(salicylaldehyde), followed by N(4)-phenylthiosemicarbazide to produce a ONS Schiff base grafted nanocomposite. Finally, by adding palladium(II) acetate, the palladium Schiff base complex was immobilized on magnetic nanocomposite. The characterization of new nanocomposites was carried out by means of several techniques such as FT-IR, XRD, FE-SEM, HRTEM, EDS, BET, VSM, XPS, DRS and TGA. The new nanocatalyst, Fe3O4@MCM-41-SB-Pd, was used in synthesis of symmetrical and unsymmetrical biaryl compounds via the Suzuki–Miyaura cross-coupling of phenylboronic acid with aryl halides. This catalyst was easily recovered by applying an external magnetic field and reused for several times without significant loss of its catalytic activity. Also the ability of synthesized mesoporous nanocomposites for enzyme immobilization was investigated and results showed that they efficiently immobilized α-amylase enzyme. Graphic Abstract: [Figure not available: see fulltext.].
- Ahmadi, Ameneh,Sedaghat, Tahereh,Azadi, Roya,Motamedi, Hossein
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- Resin encapsulated palladium nanoparticles: An efficient and robust catalyst for microwave enhanced Suzuki-Miyaura coupling
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A simple and rapid method for synthesizing highly accessible supported palladium nanoparticles inside the matrix of a commercial resin is reported. The encapsulated palladium nanoparticles were observed by TEM. The prepared catalyst has shown very high tu
- Kaur, Harjinder,Shah, Dipen,Pal, Usha
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- N-heterocyclic carbene conjugated with poly(ethylene glycol) for palladium-catalyzed Suzuki-Miyaura coupling in aqueous solvents
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Here we report a type of N-heterocyclic carbene (NHC)- and phosphine-chelated palladium catalysts with poly(ethylene glycol) (PEG) chain for Suzuki-Miyaura crosscoupling reactions. 1-(2-Diphenylphosphinoferrocenyl)- ethyl- 3-imidazolium iodides conjugated with MeO-PEG400 and MeO-PEG750, respectively, have been synthesized and characterized. It was demonstrated that the salts bearing with PEG chain could act as NHC precursors successfully under the catalytic condition to form NHC-supported palladium complexes joined by phosphine. The formed palladium complexes are highly efficient for Suzuki-Miyaura coupling of aryl bromides with phenylboronic acid at the palladium loading of 0.1 mol% in both organic and aqueous solvents.
- Shi, Ji-Cheng,Yu, Hongwei,Jiang, Dahong,Yu, Mei,Huang, Yanxian,Nong, Lanping,Zhang, Qing,Jin, Zilin
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- Hollow porous organic nanospheres for anchoring Pd(PPh3)4 through a co-hyper-crosslinking mediated self-assembly strategy
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In this work, we present a facile method for anchoring a transition metal catalyst (Pd(PPh3)4) into hollow porous organic nanospheres (H-PONs) based on a co-hyper-crosslinking mediated self-assembly strategy by using polylactide-b-polystyrene (PLA-b-PS) and Pd(PPh3)4 as precursors. The intrinsic catalytic activity of Pd(PPh3)4 could be well retained even if immobilized into H-PONs through a one-step Scholl reaction. Owing to the hierarchically porous structure, high surface area and well-dispersed active sites, the resulting H-PONs-Pd(PPh3)4 exhibited excellent catalytic activity, enhanced stability, and good recyclability for the Suzuki-Miyaura coupling in aqueous media. We hope that such a facile synthesis approach can provide a broad platform to support various transition metal catalysts anchored into hollow porous nanomaterials for the heterogeneous catalysis field.
- Gao, Shengguang,Huang, Kun,Liu, Ying,Shi, Buyin,Yu, Haitao,Zhang, Li
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- Direct Synthesis of Palladium Catalyst on Supporting WS2 Nanotubes and its Reactivity in Cross-Coupling Reactions
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Palladium nanoparticles were deposited on multiwall WS2 nanotubes. The composite nanoparticles were characterized by a variety of techniques. The Pd nanoparticles were deposited uniformly on the surface of WS2 nanotubes. An epitaxial relationship between the (111) plane of Pd and the (013) plane of WS2 was mostly observed. The composite nanoparticles were found to perform efficiently as catalysts for cross-coupling (Heck and Suzuki) reactions. The role of the nanotubes′ support in the catalytic process is briefly discussed.
- Viic, Bojana,Cohen, Hagai,Popovitz-Biro, Ronit,Tenne, Reshef,Sokolov, Viacheslav I.,Abramova, Natalya V.,Buyanovskaya, Anastasiya G.,Dzvonkovskii, Sergei L.,Lependina, Olga L.
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- The palladium(ii) complex of N,N-diethyl-1-ferrocenyl-3-thiabutanamine: Synthesis, solution and solid state structure and catalytic activity in Suzuki-Miyaura reaction
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In this paper we wish to present the first results on the synthesis of N,N-diethyl-1-ferrocenyl-3-thiabutanamine, its coordination with palladium(ii), the complete characterization of the thus obtained complex (including single crystal X-ray analysis for the complex in two polymorphic forms) and screening of its catalytic activity in Suzuki-Miyaura coupling of phenylboronic acid with several aryl bromides. The complex, either purified and then added to the reaction mixture or generated in situ, proved to be an excellent precatalyst in Suzuki-Miyaura coupling. The chemical behavior of the complex in solution was assessed by detailed NMR analyses and cyclic voltammetry measurements which allowed us to draw a number of mechanistic conclusions. This journal is
- Damljanovi, Ivan,Stevanovi, Dragana,Pejovi, Anka,Ili, Danijela,ivkovi, Marija,Jovanovi, Jovana,Vukievi, Mirjana,Bogdanovi, Goran A.,Radulovi, Niko S.,Vukievi, Rastko D.
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- Fe(OTf)3-mediated synthesis of sulfonyl dihydropyrans
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Fe(OTf)3-mediated one-pot (3+3) cycloaddition of β-ketosulfones 1 with prenyl alcohol (2) in MeNO2 affords sulfonyl dihydropyrans 5 in good yields via a sequential intermolecular α-prenylation followed by intramolecular Friedel-Crafts alkylation. The method provides a highly effective condition.
- Chang, Meng-Yang,Chen, Yu-Hsin,Cheng, Yu-Chieh
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- Fabrication of a Fe3O4@SiO2@mSiO2-HPG-COOH-Pd(0) supported catalyst and its performance in catalyzing the Suzuki cross-coupling reaction
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In this paper, magnetic Fe3O4@SiO2@mSiO2 microspheres with core-shell structure were chosen as a catalyst support, then hyperbranched polyglycerol (HPG) was successfully grafted onto the exterior surface and mesopore wall of this material under the catalysis of isopropanol aluminum. Subsequently, the terminal hydroxyl groups of HPG were successfully transformed into carboxyl groups after modification with succinic anhydride. Ultimately, palladium nanoparticles (Pd NPs) were successfully anchored onto the surface of the aforementioned magnetic Fe3O4@SiO2@mSiO2 microspheres with high density carboxylic HPG, nanocrystallization by the complexation between Pd2+ ions and carboxyl groups and the subsequent reduction, a novel Fe3O4@SiO2@mSiO2-HPG-COOH-Pd(0) supported catalyst was successfully obtained. This novel supported Pd NP catalyst is very conducive to the transference and exchange of each component in the reaction system for the orderly mesoporous opening structure. Furthermore, the introduction of a magnetism nucleus can provide convenient magnetic separation. More importantly, the numerous terminal carboxyl groups on the surface of the magnetic Fe3O4@SiO2@mSiO2 microspheres can provide plenty of sufficient binding sites for Pd NPs, and the unique hyperbranched structure is very conducive to capture uniformly dispersed nanosized palladium and can effectively enhance the catalytic activity and stability. Research indicates that this novel supported Pd NP catalyst not only possesses extremely high Pd NPs loading capacity but also shows remarkable catalytic activity to the Suzuki cross-coupling reaction between aryl halides and phenylboronic acid. Simultaneously, the catalytic activity of this supported catalyst did not show evident loss after being used at least eight times.
- Li, Wei,Tian, Yi,Zhang, Baoliang,Tian, Lei,Li, Xiangjie,Zhang, Hepeng,Ali, Nisar,Zhang, Qiuyu
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- In situ generation of supported palladium nanoparticles from a Pd/Sn/S chalcogel and applications in 4-nitrophenol reduction and Suzuki coupling
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Supported ultrafine palladium nanoparticles with uniform distribution exhibit remarkable catalytic capabilities in various applications. Obtaining size-controlled Pd nanoparticles on a support remains challenging and here we present a one-step in situ route to well-defined Pd nanoparticles through reduction of a Pd-containing chalcogel (Pd/Sn/S) with tunable size distribution. The spacings of the Pd nanoparticles on the chalcogel can be controlled by using antimony-containing chalcogels (Pd-Sb/Sn/S). The catalytic performance of Pd nanoparticles supported on the chalcogel surface was assessed in 4-nitrophenol reduction and the Suzuki-Miyaura coupling reaction, and found to exhibit good activities and robust stability. This in situ and one-step synthetic method could be further extended to synthesize a series of noble metal nanoparticles for a variety of applications.
- Shan, Xinyao,Sui, Ning,Liu, Wengang,Liu, Manhong,Liu, Jian
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- Successive C-C coupling of dienes to vicinally dioxygenated hydrocarbons: Ruthenium catalyzed [4 + 2] cycloaddition across the diol, hydroxycarbonyl, or dione oxidation levels
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The ruthenium(0) catalyst generated from Ru3(CO)12 and tricyclohexylphosphine or BIPHEP promotes successive C-C coupling of dienes to vicinally dioxygenated hydrocarbons across the diol, hydroxyketone, and dione oxidation levels to form products of [4 + 2] cycloaddition. A mechanism involving diene-carbonyl oxidative coupling followed by intramolecular carbonyl addition from the resulting allylruthenium intermediate is postulated.
- Geary, Laina M.,Glasspoole, Ben W.,Kim, Mary M.,Krische, Michael J.
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- In-situ synthesis of a palladium-polyaniline hybrid catalyst for a Suzuki coupling reaction
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Palladium-catalyzed cross-coupling reactions are one of the most frequently used synthetic tools for the construction of new carbon-carbon bonds in organic synthesis. The present study describes the use of palladium-polyaniline composite material as a catalyst for the Suzuki coupling of aryl halides. Palladium-polyaniline nanocomposite material was synthesized using an in-situ technique in which palladium acetate and aniline hydrochloride were used as the precursors of the composite. Electron microscopy imaging showed that the palladium particles were well-dispersed within the polymer matrix and were typically 3-5 nm in diameter. The metal-polymer composite material was used as a catalyst for the coupling of phenylboronic acid with aryl halides in the presence of an inorganic base and showed excellent yield with high TOF values.
- Islam, Rafique Ul,Witcomb, Michael J.,Van Der Lingen, Elma,Scurrell, Michael S.,Van Otterlo, Willem,Mallick, Kaushik
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- Bis-nickel-bridged p-terphenyl dianion - Synthesis and structures
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In this paper we present the synthesis and characterisation of novel bisnickelacyclic complexes. We carried out the reaction between 2,2′,2″,5′-tetralithio-1,1′,4′,1″-terphenyl and nickelocene in which bisnickelacyclic-dilithium complex was formed. It rep
- Buchalski, Piotr,Pacholski, Roman,Gustowski, Jan,Buchowicz, W?odzimierz,Molga, Karol,Shkurenko, Aleksander,Suwińska, Kinga
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- Organocatalytic synthesis of (Het)biaryl scaffoldsviaphotoinduced intra/intermolecular C(sp2)-H arylation by 2-pyridone derivatives
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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.
- Das, Tapas Kumar,Kundu, Mrinalkanti,Mondal, Biswajit,Ghosh, Prasanjit,Das, Sajal
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p. 208 - 218
(2021/12/29)
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- 'Awaken' aryl sulfonyl fluoride: a new partner in the Suzuki-Miyaura coupling reaction
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An example of the activation of the -SO2F group, which is traditionally considered a stable group even in the presence of a transition metal, is described using a novel partner in the Suzuki-Miyaura coupling reaction catalyzed by Pd(OAc)2 and Ruphos as ligands. The products showed good to outstanding yields and broad functional group compatibility under optimal conditions. The sequential synthesis of non-symmetric terphenyls and the gram grade process highlight the approach's synthetic utility. DFT calculations have shown that Pd0 prefers to insert between C-S bonds rather than S-F bonds. This journal is
- Ding, Chengrong,Guan, Chenfei,Miao, Huihui,Zhang, Guofu,Zhao, Yiyong
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supporting information
p. 3560 - 3564
(2022/03/07)
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- Nickel(II) complexes with N,O-donor thiopseudourea ligands: Syntheses, structures, and catalytic applications in Kumada–Corriu cross-coupling reactions
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Synthesis, characterization, and physical properties of benzyl-N′-(4-R-benzoyl)-N-(2,6-diisopropylphenyl)carbamimidothioates, HL1 (R = H) and HL2 (R = Cl), and their nickel(II) complexes having the general molecular formula [Ni(L1/2)2] (1 and 2) have been reported. Elemental analysis, magnetic susceptibility, solution electrical conductivity, and various spectroscopic (IR, UV–Vis, and 1H NMR) measurements were used to characterize HL1, HL2, and the two complexes (1 and 2). The molecular structures of all four compounds were determined by single-crystal X-ray crystallographic studies. The structures of HL1 and HL2 showed the imino-ketone form of both compounds. In each of 1 and 2, the six-membered chelate ring forming iminolate-O and azomethine-N donor two (L1/2)? ligands form a square-planar trans-N2O2 coordination environment around the metal center. The spectroscopic characteristics of HL1, HL2, 1, and 2 are consistent with their molecular structures. Both complexes were successfully employed as efficient catalysts in Kumada–Corriu C-C cross-coupling reactions of aryl bromides with phenylmagnesium bromide. The reactions provided biaryl products in good to excellent yields with a good substrate scope.
- Shakunthala, Kinche,Srivastava, Ankit Kumar,Babu, G. Narendra,Keesara, Srinivas,Pal, Samudranil
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- Porous Organic Phenanthroline-Based Polymer as an Efficient Transition-Metal-Free Heterogeneous Catalyst for Direct Aromatic C?H Activation
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Direct C?H bond transformation has been regarded as one of the most important areas in organic synthesis in both academia and industry. However, the heterogeneous transition-metal-free catalysis of direct C?H bond transformation has remained a contemporary challenge. To tackle this challenge, we designed and constructed a porous phenanthroline-based polymer (namely POP-Phen) via free radical polymerization of vinyl-functionalized phenanthroline monomers. POP-Phen shows excellent catalytic performances in transition-metal-free catalyzed C?H arylation, even better than those of the corresponding homogeneous catalyst, which is mainly attributed to the high density of catalytically active sites in the heterogeneous catalyst. Kinetic isotope experiments and spectral characterizations demonstrate the electron-transfer between the heterogeneous catalyst and the base (t-BuOK), a key step for C?H activation. We believe that this porous organic phenanthroline polymer could open a new door for the design of novel heterogeneous transition-metal-free catalysts for direct C?H activation.
- Tang, Yongquan,Chen, Fang,Wang, Sai,Sun, Qi,Meng, Xiangju,Xiao, Feng-Shou
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supporting information
p. 8684 - 8688
(2021/05/25)
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- Molecular engineered palladium single atom catalysts with an M-C1N3subunit for Suzuki coupling
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Single atom catalysis has emerged as a powerful technique for catalysis due to its outstanding performance and atom economy. Controlling the hybridization of the atom with its environment is crucial in determining the selectivity and/or yield of the reaction. However, the single atom environment is usually ill-defined and hard to predict because the pyrolysis process used in preparing SACs damages the original status of the precursors in the catalyst preparation. A molecular engineering approach to synthesize single atom catalysts (SACs) on a heterogeneous template provides a strategy to make SACs with a highly uniform coordinating environment. Herein, we report the preparation of a molecular engineered Pd single atom catalyst with a pre-defined M-N3C1 coordination (Pd-N3C1-SAC) using a structure-rigid Pd-N3C1 porphyrin as the precursor, which shows more efficient Suzuki coupling compared with the SAC with Pd-N4 coordination. The origin of the high activity of the Pd-N3C1-SAC is revealed through density functional theory calculations, where a lower reaction barrier for the rate-determining oxidative addition is identified. This journal is
- Liu, Jia,Chen, Zhongxin,Liu, Cuibo,Zhang, Bao,Du, Yonghua,Liu, Chen-Fei,Ma, Lu,Xi, Shibo,Li, Runlai,Zhao, Xiaoxu,Song, Jingting,Sui, Xin Zhi,Yu, Wei,Miao, Ling,Jiang, Jianjun,Koh, Ming Joo,Loh, Kian Ping
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supporting information
p. 11427 - 11432
(2021/05/19)
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- Efficient and Economical Preparation of Hypercrosslinked Polymers-palladium Based on Schiff Base as Recyclable Catalyst for Suzuki-Miyaura Reactions
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A novel hypercrosslinked polymer (HCP) was prepared via Friedel-Crafts alkylation reaction of Schiff base with benzene and formaldehyde dimethyl acetal (FDA) promoted by FeCl3. The HCP was then metalated with Pd(II) to form heterogeneous catalyst. The protocol featured low cost, mild conditions, readily available materials, easy separation and high yield. Physicochemical methods, including IR, N2 sorption, ICP, TGA, XPS, SEM, EDX, and TEM, were used to characterize the catalyst structure and composition. The results reveal that the heterogeneous catalyst possesses high specific surface area, large pore volume, good chemical and thermal stability, and highly dispersed palladium. The heterogeneous catalysts were applied in Suzuki-Miyaura coupling reaction to evaluate their catalytic performance. The experiments reflected that the HCPs-Pd(OAc)2 was an efficient catalyst for Suzuki-Miyaura reactions with the yield of biaryl up to 99%, while the TON could reach 2250. The reusability test showed the catalyst was easily recovered and reused for at least six times without obvious decrease in activity.
- Gao, Xiyue,Lin, Hongwei,Liu, Shasha,Luo, Qionglin,Ouyang, Yuejun,Xiang, Bailin,Xiang, Dexuan,Yao, Huan,Zhang, Li
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supporting information
p. 1879 - 1882
(2021/10/29)
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- Palladium supported on structurally stable phenanthroline-based polymer nanotubes as a high-performance catalyst for the aqueous Suzuki-Miyaura coupling reaction
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Though the Suzuki-Miyaura coupling reaction has intrinsic advantages in organic synthesis, it is still a challenging task to develop a highly active and truly heterogeneous catalyst for the aqueous Suzuki-Miyaura coupling reaction (SMR). In this work, a series of phenanthroline-based polymers (PBPs; PBP1 to PBP8) were synthesized by a simple one-step AlCl3-catalyzed Friedel-Crafts polymerization method. Systematic measurements of PBPs by N2adsorption-desorption isotherms, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA) show that most of the PBPs have a nanosheet morphology, except PBP8 which has both one-dimensional nanotubular morphology and large surface area (745 m2g?1). Benefitting from the porous nanotube morphology and the two N atoms contained in the phenanthroline unit of the polymer structure, polymer PBP8 shows adsorption effects and strong chelating stabilization on the Pd active metal (size, 2-5 nm). The Pd/PBP8 catalyst exhibits superior catalytic activity within 2 h (TOF value: 3077 h?1) and reusability (7 cycles) in the SMR with typical reactants such as bromobenzene, phenylboronic acid and the base of K3PO4.3H2O at 30 °C in a solvent mixture of water and ethanol (VH2O?:?Vethanol= 3?:?2).
- Yang, Didi,Wang, Shuhui,Dan, Ting,Gao, Dashuang,Au, Chaktong,Zhang, Wanju,Zhang, Yan
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p. 12120 - 12128
(2021/07/19)
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- Evaluation of P-bridged biaryl phosphine ligands in palladium-catalysed Suzuki-Miyaura cross-coupling reactions
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A family of biaryl phosphacyclic ligands derived from phobane and phosphatrioxa-adamantane frameworks is described. The rigid biaryl phosphacycles are efficient for Suzuki-Miyaura cross-coupling of aryl bromides and chlorides. In particular, coupling reactions of the challenging sterically hindered and heterocyclic substrates were viable at room temperature.
- Holzapfel, Cedric W.,Lamola, Jairus L.,Maumela, Munaka Christopher,Moshapo, Paseka T.
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p. 26883 - 26891
(2021/08/17)
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- Phosphonate functionalized N-heterocyclic carbene Pd(II) complexes as efficient catalysts for Suzuki-Miyaura cross coupling reaction
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A N-heterocyclic carbene (NHC) ligand, L1 bearing a pendant phosphonate ester group is used to prepare two new NHC-Pd(II) complexes, [Pd(L1)2I2] (1) and [Pd(L1)(py)I2] (2) (py = pyridine). Hydrolysis of phosphonate ester group in 2 results another Pd(II)-NHC complex, [Pd(L2)(py)I2] (3) where a phosphonic acid group is attached to the NHC ligand L2. All the three complexes are characterized by analytical and spectroscopic studies while the molecular structures of 1-2 are also determined by single crystal X-ray diffraction measurement. The catalytic efficacies of 1-3 in Suzuki-Miyaura cross coupling reactions of aryl halides and aryl boronic acid are investigated. DFT calculations were performed to decipher the role phosphonate ester or phosphonic acid substituents on the catalytic efficacy.
- Bhattacharyya, Bagmita,Kalita, Amlan Jyoti,Guha, Ankur Kanti,Gogoi, Nayanmoni
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- Preparation and characterization of cellulose sulfate/Pd nanocatalsysts with remarkable efficiency for Suzuki–Miyaura reaction
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Heterogeneous catalysis with noble metal NPs are quite attractive due to unique surface chemistry and tuneable physicochemical properties. In this work, an efficient and simple method was used to synthesize palladium nanoparticles supported on cellulose sulfate. The resulted composites were characterized using various techniques such as X-ray powder diffraction (XRD), FT-IR, energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA) to verify the chemical structure and morphological properties of nanocatalysts. Next, the synthesized catalyst was utilized in Suzuki–Miyaura reaction between aryl bronic acid and different aryl halides. The catalysis reaction was carried out under atmospheric pressure where high efficiency, unique and simple work-up procedure as well as excellent yields were achieved.
- Jokar, Mitra,Naeimi, Hossein,Nabi Bidhendi, Gholamreza
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- Anchored PdCl2 on fish scale: an efficient and recyclable catalyst for Suzuki coupling reaction in aqueous media
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PdCl2 anchored on fish scale (FS) complex were intended to a heterogeneous catalyst for ligand-free Suzuki coupling reaction in aqueous media. The catalyst FS-PdCl2 was characterized by FT-IR, powder XRD, XPS and SEM. FS-PdCl2 complex has been successfully implemented for Suzuki coupling reactions of various halogenated aromatics with arylboronic acid to provide the corresponding biaryl compounds under environmentally friendly conditions (40 °C, water solvent). Moreover, the efficient catalyst shows excellent stability and recyclability, and its catalytic activity without any decrease after 8 times consecutive reused.
- Yang, Quanlu,Yang, Fawang,Zhang, Ying,Hou, Juanjuan,Li, Jiankun,Cheng, Jinkui,Wu, Shang,Zhan, Huiying,Zhang, Xinghui,Shi, Haixiong
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supporting information
(2020/12/25)
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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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- Palladium nanoparticles encapsulated in polyimide nanofibers: An efficient and recyclable catalyst for coupling reaction
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In this study, palladium-encapsulated poly(amic acid) (Pd@PAA) nanofibers were prepared by electrospinning, followed by thermal imidization to synthesize palladium-encapsulated polyimide (Pd@PI) nanofibers. Scanning electron microscopy (SEM) images confirmed the preparation of uniform and smooth Pd@PAA and Pd@PI nanofibers. Thermogravimetric analysis (TGA) results reveal that the Pd@PI nanofibers possessed excellent thermal stability. The dispersion of palladium nanoparticles in the polyimide nanofibers was characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The catalysis results show that this Pd@PI fibrous catalyst was very efficient to catalyze the cross-coupling reactions of aromatic iodides with n-butyl acrylate (Heck reaction) or phenylboronic acid derivatives (Suzuki reaction) to afford the desired products in good to excellent yields. Moreover, the Pd@PI catalyst could be easily separated and recovered from the reaction mixture by simple filtration due to the regular fibrous structure and reused for 10 times for both Heck and Suzuki reactions without obvious loss of its initial catalytic activity. Thus, the Pd@PI nanofiber catalyst holds great potential in chemical industry in terms of its excellent catalytic activity and stability.
- Du, Yijun,Gou, Faliang,Gao, Danning,Liu, Zhifeng,Shao, Linjun,Qi, Chenze
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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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- New Nickel-Based Catalytic System with Pincer Pyrrole-Functionalized N-Heterocyclic Carbene as Ligand for Suzuki-Miyaura Cross-Coupling Reactions
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A new catalytic system with Ni(NO3)2·6H2O as the catalyst and a pincer pyrrole-functionalized N-heterocyclic carbene as the ligand was employed in the Suzuki-Miyaura cross-coupling reactions of aryl iodides with arylboronic acids. With 5 mol% catalyst, the catalytic reactions proceeded at 160 °C, giving coupling products in isolated yields of up to 94% in short reaction times (1-4 h). The system worked efficiently with aryl iodides bearing electron-donating or electron-withdrawing groups and arylboronic acids with electron-donating groups. Steric effects were observed for both aryl iodides and arylboronic acids. It is proposed that the reactions underwent a Ni(I)/Ni(III) catalytic cycle.
- Guo, Zhifo,Lei, Xiangyang
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supporting information
(2021/09/11)
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- Pd salen complex@CPGO as a convenient, effective heterogeneous catalyst for Suzuki–Miyaura and Heck–Mizoroki cross-coupling reactions
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A Pd(II) Schiff base complex supported on graphene oxide nanosheets (Pd(II) salen@CPGO) has been synthesized and characterized by FT-IR, ICP-AES, XRD, SEM/EDX and TEM. The synthesized nanocatalyst has been found to be an efficient heterogeneous catalyst for Suzuki–Miyaura and Heck–Mizoroki coupling reactions. Pd(II) salen@CPGO could be separated and recovered easily from the reaction mixture and recycled several times without a discernible decrease in its catalytic activity. The construction of a solid sheet-supported Pd catalyst would be expected to be a promising system to perform heterogeneous catalytic reactions.
- Ghabdian, Mahdieh,Nasseri, Mohammad Ali,Allahresani, Ali,Motavallizadehkakhky, Alireza
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p. 1713 - 1728
(2018/05/25)
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- Highly efficient photocatalytic Suzuki coupling reaction by Pd3P/CdS catalyst under visible-light irradiation
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Monodispersed palladium phosphide (Pd3P) (5.2 ± 0.5 nm) was firstly applied to photocatalytic Suzuki coupling reaction under visible light irradiation with CdS nanoflake as a photosensitizer. This heterogeneous system exhibited high yields to corresponding products and excellent stability in alcohol solvent at room temperature.
- Yang, Huai-Qing,Chen, Qian-Qian,Liu, Fulai,Shi, Rui,Chen, Yong
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p. 676 - 680
(2020/07/06)
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- Near-field enhancement by plasmonic antennas for photocatalytic Suzuki-Miyaura cross-coupling reactions
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It is well documented that placing a plasmonic antenna close to catalytically active nanoparticles can enhance their catalytic activity in chemical reactions via the near-field enhancement effect. Less known is whether and how the near-field enhances the reactivity of the reactant substrates involved in these reactions. Herein, we prepared an “antenna-reactor” catalyst with Au nanoparticles absorbing light as an optical antenna and the adjacent Pd nanoparticles acting as a chemical reactor to study the near-field enhancement effect in Suzuki–Miyaura cross-coupling reaction involving various substrates. The results showed that the activity of Pd nanoparticles were significantly enhanced in the presence of Au antennas. Excessively increasing the density of Au antennas, however, suppressed the reaction due to the interaction between neighboring electromagnetic hot spots. Moreover, the near-field affected different substrates in different extents, enhancing more to reactions that involve substrates with higher electron cloud density at the reactive center. The overall effect of the near-field to the catalytic reactions was proved to be an integrated result of the effect of Au nanoparticle density and reactive center electron cloud density. This study provides enriched understanding for the near-field enhancement effect in photocatalytic reactions with various substrates, and deepened insights for new “antenna-reactor” photocatalyst design.
- Han, Chenhui,Gómez, Daniel E.,Xiao, Qi,Xu, Jingsan
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p. 205 - 211
(2021/04/27)
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- Immobilization of a Pd(ii)-containing N-heterocyclic carbene ligand on porous organic polymers: efficient and recyclable catalysts for Suzuki-Miyaura reactions
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Palladium coordinated with N-heterocyclic carbene-functionalized porous organic polymers (Pd@POPs) was successfully preparedviaScholl coupling reaction and a successive immobilization method. The protocol features simple reaction conditions, easy separation, high yield and low cost. The structure and composition of Pd@POPs were characterized by N2sorption, TGA, FT-IR, SEM, EDX, TEM, XPS and ICP. Then the obtained heterogeneous catalysts were applied in Suzuki-Miyaura coupling reaction to evaluate their catalytic performance. The Pd@POPs displayed high catalytic activity for the Suzuki-Miyaura coupling reaction in an EtOH/H2O solvent. A 0.03 mol% Pd loading was sufficient for the reaction with a high turnover number (TON) of 3220. Moreover, the catalyst was easily recovered and reused for at least six consecutive cycles without obvious loss of its initial activity.
- Gao, Xiyue,Lin, Hongwei,Liu, Cijie,Luo, Qionglin,Ouyang, Yuejun,Xiang, Bailin,Xiang, Dexuan,Yao, Huan,Zhou, Nonglin
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p. 3676 - 3680
(2021/06/17)
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- Functionalized chitosan as a novel support for stabilizing palladium in Suzuki reactions
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Chitosan is a versatile polysaccharide in different domains due to facile modification and good biodegradability. In this paper, taking advantage of such functional properties, we have developed a stabilizer agent [OCMCS-SB] produced from chitosan, and palladium was successfully immobilized on this designed stabilizer [OCMCS-SB-Pd(II)]. The obtained complex was illuminated by 13C CP-MAS NMR, FT-IR, TGA, XRD, XPS, SEM, TEM and ICP-OES analyses. Due to the interactions of primary hydroxyl groups on chitosan, Schiff base and carboxy groups, the Pd complex showed excellent reactivity (up to 99 %) and stability towards Suzuki reactions in eco-friendly medium. Subsequently, the reusability experiments for OCMCS-SB-Pd(II) formed from chitosan were examined in five consecutive cycles, which showed no appreciable decrease in activity. Furthermore, a reasonably trifunctional complex structure was proposed. The present bio-based system offers a promising approach in utilizing such biopolymers in organic transformations.
- Dong, Yahao,Bi, Jiajun,Ming, Shujun,Zhang, Shoute,Zhu, Dajian,Meng, Di,Li, Tao
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- Efficient visible-light-driven Suzuki coupling reaction over Co-doped BiOCl/Ce-doped Bi2O2CO3composites
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Suzuki coupling reaction is a widely practiced protocol in organic synthesis for the formation of C-C bonds. The conventional process for this reaction usually involves high temperatures and noble metals. Hence, the development of a green, cost-effective photocatalytic system is an attractive and challenging strategy for the reaction. Here, we report a modified palladium-free Co-doped BiOCl/Ce-doped Bi2O2CO3(CBCB) composite, which shows high photocatalytic activity under white LED irradiation. At room temperature, an excellent yield (91%) of the desired cross-coupling product biphenyl was obtained in environmentally friendly solvents. Density functional calculations, together with the experimental results, show that the presence of Co and Ce ions results in the appearance of some impurity levels near the Fermi level of pure BiOCl and Bi2O2CO3, which decreases their forbidden bandwidth, thus ensuring higher light absorption and superior electronic conductivity. Moreover, the intimate interfacial contact between Co-doped BiOCl and Ce-doped Bi2O2CO3planes has a significant impact on the separation and transfer of photoinduced charge carriers, which ultimately leads to a remarkable increase in visible-light-driven photocatalytic activity.
- Zhao, Dan-Xia,Lu, Guo-Ping,Cai, Chun
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supporting information
p. 1823 - 1833
(2021/03/09)
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- 2-Phosphinoimidazole Ligands: N-H NHC or P-N Coordination Complexes in Palladium-Catalyzed Suzuki-Miyaura Reactions of Aryl Chlorides
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We report the synthesis of two palladium 2-(dialkylphosphino)imidazole complexes and demonstrate their activity as catalysts for Suzuki-Miyaura reactions with (hetero)aryl chlorides at room temperature. Our mechanistic studies demonstrate that these palladium complexes exist as an equilibrium mixture between the P-N coordinated and N-H NHC forms of ligand. Our studies suggest that the N-H NHC form may be important for high catalytic activity in Suzuki-Miyaura reactions with aryl chlorides. These reactions proceed at or near room temperature in good to excellent yields. Heteroaryl chlorides are also reactive at lower catalyst loadings.
- Martinez, Erin E.,Larson, Alexandra J. S.,Fuller, Sydney K.,Petersen, Kathryn M.,Smith, Stacey J.,Michaelis, David J.
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supporting information
p. 1560 - 1564
(2021/05/29)
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- Oxidative Sulfonylation of Hydrazones Enabled by Synergistic Copper/Silver Catalysis
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A copper/silver-cocatalyzed protocol for oxidative sulfonylation of hydrazones is demonstrated. A wide range of β-ketosulfones and N-acylsulfonamides are directly synthesized in moderate to good yields. Our work provides a viable method for scalable preparation of β-ketosulfone derivatives that have found wide applications in the pharmaceutical industry.
- Xu, Jun,Shen, Chao,Qin, Xian,Wu, Jie,Zhang, Pengfei,Liu, Xiaogang
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p. 3706 - 3720
(2021/02/05)
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- Pd-NHCs Enabled Suzuki-Miyaura Cross-Coupling of Arylhydrazines via C–N Bond Cleavage
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We describe a highly efficient protocol for cross-coupling of phenylhydrazines with arylboronic acids by Pd-NHCs under aerobic reaction condition. A series of well-defined Pd-NHCs complexes were evaluated and the relationship between the structure and the catalytic properties was investigated. It was disclosed that the Pd-PEPPSI-IPr proved to be the robust precatalyst, providing access to a range of (hetero)biaryls in good to excellent yields.
- Zeng, Xiao-Xiao,Li, Dong-Hui,Zhou, Zhen,Xu, Chang,Liu, Feng-Shou
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supporting information
(2021/03/01)
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- Lipids as versatile solvents for chemical synthesis
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Development of safe, renewable, cheap and versatile solvents is a longstanding challenge in chemistry. We show here that vegetable oils and related systems can become prominent solvents for organic synthesis. Suzuki-Miyaura, Hiyama, Stille, Sonogashira and Heck cross-couplings proceed with quantitative yields in a range of vegetable oils, fish oil, butter and waxes used as solvents. Appropriate methodologies for high-throughput screening and sustainable isolation techniques applicable for vegetable oils and related lipids are presented.
- Bayer, Annette,Gevorgyan, Ashot,Hopmann, Kathrin H.
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supporting information
p. 7219 - 7227
(2021/09/28)
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- Surface engineered Iridium-based magnetic photocatalyst paving a path towards visible light driven C-H arylation and cyanation reaction
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The report presents the fabrication and application of a highly versatile, magnetic and robust iridium based photoredox nanocatalyst. Herein, Ir(PPy)3 based photocatalyst sites have been chemically engineered over the magnetic nanoparticles to encompass the captivating features of homogeneous iridium photocatalyst with the magnetically recyclable core. A household photoreactor was designed and fabricated to achieve highly selective visible light driven oxidative C-H arylation and C-H cyanation under sustainable and ambient reaction conditions utilizing the Ir@PyBz@ASMNPs photoredox nanocatalyst. The environment friendly Ir@PyBz@ASMNPs shows excellent photocatalytic activity, broad substrate adaptability and outstanding recyclability compared to the analogous homogeneous catalysts. Indeed, the Ir@PyBz@ASMNPs possess some key features including high surface area, high iridium metal loading and excellent stability. This work is expected to enlighten and provide new insights in the rational design of high performance and recoverable photoredox nanocatalyst through surface engineering strategy.
- Gaur, Rashmi,Gawande, Manoj B.,Kaushik, Bhawna,Rana, Pooja,Sharma, Priti,Sharma, Rakesh K.,Yadav, Priya,Yadav, Sneha
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p. 297 - 308
(2021/08/23)
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- Nickel- and Palladium-Catalyzed Cross-Coupling Reactions of Organostibines with Organoboronic Acids
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A strategy for the formation of antimony-carbon bond was developed by nickel-catalyzed cross-coupling of halostibines. This method has been applied to the synthesis of various triaryl- and diarylalkylstibines from the corresponding cyclic and acyclic halostibines. This protocol showed a wide substrate scope (72 examples) and was compatible to a wide range of functional groups such as aldehyde, ketone, alkene, alkyne, haloarenes (F, Cl, Br, I), and heteroarenes. A successful synthesis of arylated stibine 3 a in a scale of 34.77 g demonstrates high synthetic potential of this transformation. The formed stibines (R3Sb) were then used for the palladium-catalyzed carbon–carbon bond forming reaction with aryl boronic acids [R?B(OH)2], giving biaryls with high selectivity, even the structures of two organomoieties (R and R′) are very similar. Plausible catalytic pathways were proposed based on control experiments.
- Zhang, Dejiang,Le, Liyuan,Qiu, Renhua,Wong, Wai-Yeung,Kambe, Nobuaki
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supporting information
p. 3104 - 3114
(2020/12/11)
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- Efficient photocatalytic chemoselective and stereoselective C-C bond formation over AuPd@N-rich carbon nitride
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Heterogeneous chemoselective or stereoselective C-C coupling reactions remain extremely challenging in traditional organic synthesis. Here, we constructed a AuPd@N-rich carbon nitride (NRCN) photocatalyst through simple ammonia solution heat treatment of carbon nitride and then AuPd NP loading. AuPd@NRCN exhibited extraordinary light color promoted catalytic performance in C-C bond formation under visible light in air. Surprisingly, both high chemoselectivity to unsymmetrical Ullmann biaryl products and satisfactory stereoselectivity to Z-type Heck reaction products could be achieved by changing the light source color. Various substrates exhibited great potential for the economical synthesis of unsymmetrical biaryl products and Z-type olefins. Efficient visible light promoted C-I bond activation accompanied with improved photocatalytic coupling reaction efficiency over AuPd@NRCN was verified firstly by in situ DRIFTS. Considering that the Ullmann cross-coupling reaction is a multi-photon reaction, the improved photocatalytic performance in the Ullmann cross-coupling reaction using a combination of light sources with different colors might be due to the activation of different substrates and/or steps requiring different energies, and the combination of the two energy sources was beneficial for improving the activation efficiency of different substrates and/or steps. The activation of iodobenzene and styrene in the Heck reaction with light was also beneficial to the formation of the stilbene product. The light color promoted chemoselectivity and stereoselectivity are expected to have profound impact on organic synthetic methodology improvement. This journal is
- Jiang, Heyan,Xu, Jie,Zhang, Sishi,Cheng, Hongmei,Zang, Cuicui,Bian, Fengxia
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p. 219 - 229
(2021/01/28)
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- Cobalt-Catalyzed Coupling of Aryl Chlorides with Aryl Boron Esters Activated by Alkoxides
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The cobalt-catalyzed Suzuki biaryl cross-coupling of aryl chloride substrates with aryl boron reagents, activated with more commonly used bases, remained a significant unmet challenge in the race to replace platinum group metal catalysts with Earth-abundant metal alternatives. We now show that this highly desirable process can be realized using alkoxide bases, provided the right counterion is employed, strict stoichiometric control of the base is maintained with respect to the aryl boron reagent, and the correct boron ester is selected. Potassium tert-butoxide works well, but any excess of the base first inhibits and then poisons the catalyst. Lithium tert-butoxide performs very poorly, while even catalytic amounts of lithium additives also poison the catalyst. Meanwhile, a neopentane diol-based boron ester is required for best performance. As well as delivering this sought-after transformation, we have undertaken detailed mechanistic and computational investigations to probe the possible mechanism of the reaction and help explain the unexpected experimental observations.
- Tailor, Sanita B.,Manzotti, Mattia,Smith, Gavin J.,Davis, Sean A.,Bedford, Robin B.
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p. 3856 - 3866
(2021/04/07)
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- Feeding Carbonylation with CO2via the Synergy of Single-Site/Nanocluster Catalysts in a Photosensitizing MOF
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Solar-driven carbonylation with CO2 replacing toxic CO as a C1 source is of considerable interest; however it remains a great challenge due to the inert CO2 molecule. Herein, we integrate cobalt single-site and ultrafine CuPd nanocluster catalysts into a
- Fu, Shanshan,Guo, Guang-Chen,Guo, Song,Lu, Tong-Bu,Yao, Shuang,Yuan, Wenjuan,Zhang, Zhi-Ming
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p. 20792 - 20801
(2021/12/14)
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- Small organic molecules with tailored structures: Initiators in the transition-metal-free C-H arylation of unactivated arenes
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Simple, small organic molecules containing nitrogen and oxygen atoms in their structures have been disclosed to catalyze transition-metal-free C-H arylation of unactivated arenes with aryl iodides in the presence of tBuOK. In this article, an optimized catalytically active molecule, (2-(methylamino)phenyl)methanol, was designed. A broad range of aryl iodides could be converted into the corresponding arylated products at 100 °C over 24 h with good to excellent yields. Mechanistic experiments verified that radicals participated in this catalytic transformation and that the cleavage of the aromatic C-H bond was not the rate determining step. A K+ capture experiment by 18-crown-6 emphasized the significance of the cation species of the strong base. Fourier transform infrared spectroscopy proved that the catalytic system was activated by the hydrogen bonds between small organic molecules and tBuOK. Also, a clear mechanism was proposed. This transition-metal-free method affords a promising system for efficient and inexpensive synthesis of biaryls via a user-friendly approach, as confirmed by scale-up experiments.
- Chen, Suqing,Chen, Wenjun,Chen, Yu,Liu, Zhenghui,Mu, Tiancheng,Wang, Peng,Yan, Zhenzhong
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p. 14500 - 14509
(2020/04/27)
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- Ligand-free Suzuki coupling reaction with highly recyclable ionic palladium catalyst, Ti1-xPdxO2-x (x?=?0.03)
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We synthesized a recyclable palladium ionic catalyst, Ti0.97Pd0.03O1.97, using a solution combustion method (SCM), and characterized by XRD and Rietveld refinement. The synthesized Pd ionic catalyst is stable, insensitive to moisture and air, and easy to handle. The new catalyst has exhibited a phenomenal result for the Suzuki-Miyaura cross-coupling reaction with a broad substrate scope, and the reaction proceeds in an aqueous medium. The new catalyst proved beneficial and produced excellent yields irrespective of aryl halide used in the reaction (electron-rich or electron-poor or heterocyclic compounds) and shown a turnover frequency (TOF) of 14–25 h?1 for different reactions. The catalyst was coated on a cordierite monolith (Mg2Al4Si5O18), which enhanced the applicability of the catalyst, and made the handling and recycling of the catalyst very easy. Suzuki Miyaura reaction was carried out using both Pd-powder catalysts as well as the Pd-coated honeycomb, which gave almost similar results. We have demonstrated the recyclability of Pd coated cordierite monolith and shown the superiority of the catalyst over the other Pd catalysts for the Suzuki-Miyaura reaction.
- Bhat K, Shrikanth,Lanke, Veeranjaneyulu,Prasad, Jagadeesh Dasappa,Prabhu, Kandikere Ramaiah
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- Palladium supported on triazolyl-functionalized hypercrosslinked polymers as a recyclable catalyst for Suzuki-Miyaura coupling reactions
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A novel hypercrosslinked polymers-palladium (HCPs-Pd) catalyst was successfully preparedviathe external cross-linking reactions of substituted 1,2,3-triazoles with benzene and formaldehyde dimethyl acetal. The preparation of HCPs-Pd has the advantages of low cost, mild conditions, simple procedure, easy separation and high yield. The catalyst structure and composition were characterized by N2sorption, TGA, FT-IR, SEM, EDX, TEM, XPS and ICP-AES. The HCPs were found to possess high specific surface area, large micropore volume, chemical and thermal stability, low skeletal bone density and good dispersion for palladium chloride. The catalytic performance of HCPs-Pd was evaluated in Suzuki-Miyaura coupling reactions. The results show that HCPs-Pd is a highly active catalyst for the Suzuki-Miyaura coupling reaction in H2O/EtOH solvent with TON numbers up to 1.66 × 104. The yield of biaryls reached 99%. In this reaction, the catalyst was easily recovered and reused six times without a significant decrease in activity.
- Lin, Hongwei,Liu, Cijie,Liu, Shasha,Luo, Qionglin,Ouyang, Yuejun,Shu, You,Xiang, Dexuan,Xu, Wei,Zheng, Lijuan
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p. 17123 - 17128
(2020/05/18)
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- Palladium Immobilized on 2,2′-Dipyridyl-Based Hypercrosslinked Polymers as a Heterogeneous Catalyst for Suzuki–Miyaura Reaction and Heck Reaction
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Abstract: 2,2′-Bipyridine was successfully integrated into the skeleton of hypercrosslinked polymers networks (HCPs-bipy) via Friedel–Crafts reaction and Scholl coupling reaction, and PdCl2 was locked in this network polymers by coordination with pyridine motif. The preparation of HCPs-bipy has the advantages of low cost, mild conditions, easy separation and high yield. FT-IR, TGA, N2 sorption, ICP, XPS, SEM, EDX and TEM was employed to characterize the structure and composition of the heterogeneous catalysts. The result indicates that HCPs-bipy-Pd possess high specific surface areas, large microporous volume, thermal stability, and highly dispersion of palladium species. HCPs-bipy-Pd can be applied in Suzuki–Miyaura reactions and Heck reactions as robust heterogeneous catalyst to afford high yield. The reusability test demonstrates that HCPs-bipy-Pd could be recovered and reused for at least five times without losing catalytic activity. Graphic Abstract: [Figure not available: see fulltext.].
- Liu, Cijie,Xu, Wei,Xiang, Dexuan,Luo, Qionglin,Zeng, Shunqin,Zheng, Lijuan,Tan, Yujie,Ouyang, Yuejun,Lin, Hongwei
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p. 2558 - 2565
(2020/03/23)
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- Ultrafine Pd nanoparticles loaded benzothiazole-linked covalent organic framework for efficient photocatalytic C-C cross-coupling reactions
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We proposed a strategy that a benzothiazole-linked covalent organic framework (TTT-COF) was used as a substrate to prepare metal composite photocatalyst Pd NPs?TTT-COF. Firstly, benzothiazole linked TTT-COF exhibited superior chemical stability and photoresponse. Moreover, a finer particle size (2.01 nm) and more uniform distribution of Pd NPs were observed in Pd NPs?TTT-COF owing to the binding interaction between Pd NPs and S in benzothiazole groups. Pd NPs?TTT-COF exhibited superior efficiency and reusability in photocatalytic C-C cross-coupling reactions. Mechanism study suggested that photogenerated electrons and holes on TTT-COF played important roles in these reactions. This journal is
- Cai, Yaqi,Niu, Hongyun,Xu, Lin,Yang, Yongliang,Zhang, Hui,Zhao, Weijia
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p. 29402 - 29407
(2020/10/02)
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- An effective photothermal dual-responsive Pd1Cu4/Ce: XOy catalyst for Suzuki-Miyaura coupling reactions under mild conditions
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The Suzuki-Miyaura coupling reaction is one of the effective methods for forming C-C bonds in modern organic synthesis. However, most of the current catalysts can only effectively catalyze the aryl iodides and aryl bromides, and the catalytic activity for the inexpensive aryl chlorides is relatively low. Herein, the Pd1Cu4/CexOy catalysts can not only exhibit excellent performance in the conventional thermal reactions of aryl bromides and arylboronic acids, but also effectively activate aryl chlorides in Suzuki-Miyaura coupling reactions under visible light irradiation at room temperature. The CexOy carriers can provide photogenerated electrons to enrich the electron density of the Pd nanoparticles, which can effectively activate the strong C-Cl bonds of the aryl chlorides. Meanwhile, the photogenerated holes of CexOy can activate arylboronic acids. The presence of Pd and Cu2O can further enhance the absorption of visible light by CexOy. Catalysts prepared in this work could provide a great promise for using inexpensive metals to synergistically catalyze Suzuki-Miyaura coupling reactions under mild conditions.
- Liu, Bo,Xu, Tong,Li, Chunping,Bai, Jie
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p. 3794 - 3801
(2020/03/17)
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- Pyridine-based hypercrosslinked polymers as support materials for palladium photocatalysts and their application in Suzuki-Miyaura coupling reactions
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A series of hypercrosslinked polymers (P1 to P8) was synthesized from pyridine and conjugated monomers to support palladium for photocatalytic Suzuki-Miyaura coupling reactions. The results of SEM, TEM and XRD analyses reveal that the supports possess a loose porous amorphous lamellar structure, and the TGA test shows that they are thermally stable. Among the prepared photocatalysts, the one using P6 as a support performed the best, displaying excellent photocatalytic and recycling performance under the irradiation of blue light at 30 °C.
- Zhang, Yan,Zhang, Le,Zhang, Xiaoli,Yang, Didi,Du, Cheng,Wan, Liu,Au, Chaktong,Chen, Jian,Xie, Mingjiang
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p. 15202 - 15208
(2020/09/23)
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- Anchoring Pd(OAc)2 on amide-bonded covalent organic frameworks: An efficient heterogeneous Pd@OC-MA catalyst for Suzuki-Miyaura coupling reactions in water
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Nitrogen-rich of a melamine-based mesoporous covalent organic frameworks (COFs) materials were synthesized and used as a carrier to support a Pd(OAc)2. The Pd@OC-MA revealed an efficient catalytic activity and selectivity for Suzuki-Miyaura coupling reactions in an environmentally friendly water medium at room temperature. Specifically, it had moderate to excellent conversion for inactive chlorinated aromatic hydrocarbons. The catalyst was synthesized simply, had high stability and good selectivity, and was easy to recycle. Excellent catalytic activity of the Pd@OC-MA was also observed after five consecutive cycles.
- Wu, Shang,Zhang, Ying,Jiang, Hongyan,Wu, Lan,Ding, Ning,Jiang, Pengwei,Zhang, Hong,Zhao, Lianbiao,Yin, Fenping,Yang, Quanlu
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supporting information
(2020/11/02)
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- Magnetically recoverable 2-(aminomethyl)phenols-modified nanoparticles as a catalyst for Knoevenagel condensation and carrier for palladium to catalytic Suzuki coupling reactions
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A class of magnetic nanoparticles modified by 2-(aminomethyl)phenols has been successfully designed and synthesized as a reusable catalyst for Knoevenagel reaction. What's more, such nanomaterial also proved as suitable carrier for immobilization of palladium nanoparticles and the obtained composite exerted potent catalytic activity in Suzuki coupling reactions. Both of the (aminomethyl)phenols-modified nanoparticles and its related palladium nanocatalyst could be easily separated and reused for several consecutive runs by magnetic decantation without significant loss of their catalytic efficiency.
- Wang, Gongshu,Ding, Zhiqiang,Meng, Lingxin,Yan, Guiyang,Chen, Zhangpei,Hu, Jianshe
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- Photoaccelerated energy transfer catalysis of the Suzuki-Miyaura coupling through ligand regulation on Ir(iii)-Pd(ii) bimetallic complexes
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Three bimetallic Ir(iii)-Pd(ii) complexes [Ir(ppy)2(bpm)PdCl2](PF6) (ppy = 2-phenylpyridine, 1), [Ir(dfppy)2(bpm)PdCl2](PF6) (dfppy = (4,6-difluorophenyl)pyridine, 2), and [Ir(pq)2(bpm)PdCl2](PF6) (pq = 2-phenylquinoline, 3) were synthesized by using 2,2′-bipyrimidine (bpm) as a bridging ligand. The influences of the cyclometalated ligand at the Ir(iii) center on the photophysical and electrochemical properties as well as photocatalytic activity for the Suzuki-Miyaura coupling reaction under mild conditions were evaluated. The results revealed that complex 3 enables dramatically accelerating the Suzuki-Miyaura coupling reaction under visible light irradiation at room temperature, due to the effective absorption of visible light and appropriate locus of the excited chromophore. Mechanism studies showed that the chromophore [Ir(pq)2(bpm)] fragment absorbs visible light to produce the triplet excited state centering on the bridging ligand which boosts the formation of electron rich Pd(ii) units and facilitates the oxidative addition step of the catalytic cycle. Simultaneously, the excited chromophore undergoes energy transfer efficiently to the Pd(ii) reaction site to form the excited Pd(ii) species, resulting in enhancement of Pd(ii) reduction steps of the Suzuki-Miyaura coupling reaction and increasing the reactivity of the catalyst. This provides a new strategy for designing photocatalysts for coupling reaction through altering the cyclometalated ligand to modulate the photophysical properties and the cooperation between two metal units.
- Cao, Man-Li,Yao, Su-Yang,Zhang, Xiu-Lian
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p. 42874 - 42882
(2020/12/22)
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- Pd nanoparticles supported on amphiphilic porous organic polymer as an efficient catalyst for aqueous hydrodechlorination and Suzuki-Miyaura coupling reactions
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Developing efficient and recyclable heterogeneous catalysts for organic reactions in water is important for the sustainable development of chemical industry. In this work, Pd nanoparticles supported on DABCO-functionalized porous organic polymer was successfully prepared through an easy copolymerization and successive immobilization method. Characterization results indicated that the prepared catalyst featured big surface area, hierarchical porous structure, and excellent surface amphiphilicity. We demonstrated the use of this amphiphilic catalyst in two case reactions, i.e. the aqueous hydrodechlorination and Suzuki-Miyaura coupling reactions. Under mild reaction conditions, the catalyst showed high catalytic activities for the two reactions. In addition, the catalyst could be easily recovered and reused for several times. Also, no obvious Pd leaching and aggregation of Pd nanoparticles occurred up during the consecutive reactions.
- Lei, Yizhu,Zhu, Wenchao,Wan, Yali,Wang, Renshu,Liu, Hailong
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- A catalytic system with high efficiency and recyclability based on Suzuki and Heck reaction in aqueous admicellar medium
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A recyclable and non-phosphine solid palladium (II) catalyst was prepared and characterized by HR-MS, FT-IR, XPS, EDS, TGA, SEM, TEM and ICP. The Pd-catalyst exhibited high-performance catalytic activity in Suzuki and Heck C-C coupling reactions in an environmentally benign water medium. Further, the Pd-catalyst (Z4) can be reused for 15 times with little decrease of activity through simple and efficient recovery. In addition, the turn-over number (TON) of Pd- catalyst can reach 380 at room temperature. These results proved that the Pd-catalyst has a stable structure and can be recycled many times, making the process sustainable.
- Zhang, Hao,Zhu, Ji-Hua,Hou, Fei,Quan, Zheng-Jun,Wang, Xi-Cun
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- Facile fabrication of magnetically separable palladium nanoparticles supported on modified kaolin as a highly active heterogeneous catalyst for Suzuki coupling reactions
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In this study, Fe3O4 loaded Schiff base modified kaolin was prepared as a new support and palladium nanoparticles were anchored on it without any additional reducing agent (Pd NPs&at;Kao/Fe3O4/Pyr). Characterization studies demonstrated that Pd NPs&at;Kao/Fe3O4/Pyr was successfully designed and the size of particles was about 25 nm. Pd NPs&at;Kao/Fe3O4/Pyr was then utilized as catalyst in the preparation of biaryl compounds via Suzuki cross coupling reactions. Catalytic tests showed that Pd NPs&at;Kao/Fe3O4/Pyr acted as a highly active heterogeneous nanocatalyst in the coupling reaction of aryl iodides, bromides and chlorides containing different functional groups. Moreover, it was found that Pd NPs&at;Kao/Fe3O4/Pyr was successfully used in consecutive recycling tests and gave an 89percent yield even after ten runs. In addition to the high catalytic behavior and reusability, Pd NPs&at;Kao/Fe3O4/Pyr have some advantages such as i) capability of application for various halides containing different functional groups, ii) ease of purification of final product and iii) simple work-up.
- Baran, Talat,Nasrollahzadeh, Mahmoud
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- High photocatalytic activity of a NiO nanodot-decorated Pd/SiC catalyst for the Suzuki-Miyaura cross-coupling of aryl bromides and chlorides in air under visible light
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The Suzuki-Miyaura cross-coupling reaction is an effective process for C-C bond formation in organic synthesis. Herein, we report a NiO nanodot-decorated Pd/SiC catalyst, synthesized by atomic layer deposition, which shows high photocatalytic activity for the Suzuki-Miyaura coupling of both aryl bromides and chlorides with phenylboronic acid at 30 °C in air. The Mott-Schottky contact in SiC/Pd enhances the rapid transfer of the photogenerated electrons from SiC to Pd nanoparticles. Moreover, the energy different between the highest occupied molecular orbital of the ultrafine NiO nanodots and the Fermi level of Pd forces a spontaneous electron transfer from NiO to Pd. As a result, the concentrated electrons in the Pd nanoparticles can facilitate the cleavage of C-Br or C-Cl bonds, which normally requires rather high temperatures in thermal processes. The holes left on the SiC support can assist the cleavage of the C-B bond.
- Braunschweig, Holger,Guo, Xiang-Yun,Guo, Xiao-Ning,Hao, Cai-Hong,Jiao, Zhi-Feng,Marder, Todd B.,Qiao, Yan,Qin, Yong,Radius, Udo,Tian, Ya-Ming,Wang, Ying-Xiong,Zhang, Bin
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p. 517 - 524
(2020/07/21)
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- A simple, efficient and green approach for the synthesis of palladium nanoparticles using Oxytocin: Application for ligand free Suzuki reaction and total synthesis of aspongpyrazine A
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A novel, green, eco-friendly and cost-effective biological route for the synthesis of palladium nanoparticles (PdNPs) from commercially available palladium chloride and easily isolable hormone Oxytocin as reducing agent is reported here. Characterization of PdNPs were done using various techniques, UV–visible spectroscopy, XRD, TEM and EDAX, characterization data confirmed the formation of Pd0 from Pd2+. The size of synthesized PdNPs were 15–20 nm. The scope of Pd nanoparticles was studied for the C–C bond formation Suzuki reaction. The catalytic activity of PdNPs was excellent in short reaction time and reaction works in green solvent water as well as catalyst can be recycled. Simple and efficient approach for total synthesis of aspongpyrazine A of the recently isolated natural substance is described.
- Bendre, Ameya D.,Kodam, Kisan M.,Patil, Viraj P.,Terdale, Santosh S.,Waghmode, Suresh B.
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supporting information
(2020/01/13)
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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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- Anchoring Positively Charged Pd Single Atoms in Ordered Porous Ceria to Boost Catalytic Activity and Stability in Suzuki Coupling Reactions
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Single-atom (SA) catalysis bridging homogeneous and heterogeneous catalysis offers new opportunities for organic synthesis, but developing SA catalysts with high activity and stability is still a great challenge. Herein, a heterogeneous catalyst of Pd SAs anchored in 3D ordered macroporous ceria (Pd-SAs/3DOM-CeO2) is developed through a facile template-assisted pyrolysis method. The high specific surface area of 3DOM CeO2 facilitates the heavily anchoring of Pd SAs, while the introduction of Pd atoms induces the generation of surface oxygen vacancies and prevents the grain growth of CeO2 support. The Pd-SAs/3DOM-CeO2 catalyst exhibits excellent activity toward Suzuki coupling reactions for a broad scope of substrates under ambient conditions, and the Pd SAs can be stabilized in CeO2 in long-term catalytic cycles without leaching or aggregating. Theoretical calculations indicate that the CeO2 supported Pd SAs can remarkably reduce the energy barriers of both transmetalation and reductive elimination steps for Suzuki coupling reactions. The strong metal-support interaction contributes to modulating the electronic state and maintaining the stability of Pd SA sites. This work demonstrates an effective strategy to design and synthesize stable single-atom catalysts as well as sheds new light on the origin for enhanced catalysis based on the strong metal-support interactions.
- Tao, Xueqin,Long, Ran,Wu, Di,Hu, Yangguang,Qiu, Ganhua,Qi, Zeming,Li, Benxia,Jiang, Ruibin,Xiong, Yujie
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- Palladium Supported on Silk Fibroin for Suzuki–Miyaura Cross-Coupling Reactions
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Silk fibroin supported Pd (Pd/SF) has been prepared and used as catalyst in Suzuki–Miyaura cross-coupling reactions in water/ethanol (4:1 v/v) mixture. The reactions proceed rapidly with aryl iodides and boronic acids with different electronic properties using low metal loading (0.38 mol-%). Pd/SF exhibits better recyclability compared to other biopolymer-supported Pd catalysts, up to nineteen cycles without loss of activity.
- Albano, Gianluigi,Farinola, Gianluca M.,Lo Presti, Marco,Milella, Antonella,Omenetto, Fiorenzo G.,Rizzo, Giorgio
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supporting information
p. 6992 - 6996
(2020/11/30)
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- Synthesis of Enaminone-Pd(II) Complexes and Their Application in Catalysing Aqueous Suzuki-Miyaura Cross Coupling Reaction
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A series of Pd(II)-enaminone complexes, termed Pd(eao)2, have been synthesized and characterized. The investigation on the catalytic activities of these new Pd(II)-reagents has proved that the Pd(eao)2-1 possesses excellent catalytic activity for the Suzuki- Miyaura cross coupling reactions of aryl bromides/chlorides with aryl/vinyl boronic acids in the environmentally benign media of aqueous PEG400 at low loading (5 mol‰). The superiority of this Pd(II)-reagent to those commercial Pd(II) and Pd(0) catalysts in catalyzing the reactions has been confirmed by parallel experiments. What's more, Pd(eao)2-2 has been found as a practical catalyst for the homo-coupling reactions of aryl boronic acids.
- Fu, Leiqing,Cao, Xiaoji,Wan, Jie-Ping,Liu, Yunyun
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p. 254 - 258
(2020/01/25)
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