scholarly journals Study of Deactivation in Suzuki Reaction of Polymer-Stabilized Pd Nanocatalysts

Processes ◽  
2020 ◽  
Vol 8 (12) ◽  
pp. 1653
Author(s):  
Linda Nikoshvili ◽  
Elena S. Bakhvalova ◽  
Alexey V. Bykov ◽  
Alexander I. Sidorov ◽  
Alexander L. Vasiliev ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Catalyst Deactivation ◽  
Phenylboronic Acid ◽  
Suzuki Reaction ◽  
Cross Coupling ◽  
Catalyst Stability ◽  
Separation Procedure ◽  
Amino Groups ◽  
Highly Active ◽  
Hydrophobic Nature

This work is addressed to the phenomenon of catalyst deactivation taking place during the repeated uses in the reaction of Suzuki-Miyaura (S-M) cross-coupling, which is widely applied in industry for C-C bond formation. Ligandless catalysts based on Pd(0) NPs supported on hyper-cross-linked polystyrene (HPS) of two types (non-functionalized and bearing tertiary amino groups) were studied in a model S-M reaction between 4-bromoanisole and phenylboronic acid. Synthesized catalysts were shown to be highly active under mild reaction conditions. HPS allows stabilization of Pd(0) NPs and prevents their agglomeration and detectable Pd leaching. However, the loss of catalytic activity was observed during recycling. The deactivation issue was assigned to the hydrophobic nature of non-functionalized HPS, which allowed a strong adsorption of cross-coupling product during the catalyst separation procedure. A thorough washing of Pd/HPS catalyst by hydrophobic solvent was found to improve to the big extent the observed catalytic activity, while the replacement of non-functionalized HPS by a one containing amino groups increased the catalyst stability at the expense of their activity.

scholarly journals INFLUENCE OF THE AROMATIC POLYMERIC MATRIX TYPE ON STABILITY OF NANOSIZED PALLADIUM CATALYSTS IN SUZUKI REACTION

2020 ◽  
pp. 775-783
Author(s):  
Елена Сергеевна Бахвалова ◽  
Алексей Владимирович Быков ◽  
Александр Иванович Сидоров ◽  
Линда Жановна Никошвили ◽  
Lioubov Kiwi-Minsker
Keyword(s):  
Palladium Catalysts ◽  
Aryl Halide ◽  
Phenylboronic Acid ◽  
Suzuki Reaction ◽  
Cross Coupling ◽  
Polymeric Matrix ◽  
Catalyst Stability ◽  
Water Mixture ◽  
Strong Adsorption ◽  
Crosslinked Polystyrene

Данная работа посвящена исследованию влияния типа полимерной матрицы сверхсшитого полистирола на активность и стабильность палладиевых катализаторов кросс-сочетания Сузуки. Показано, что применение сверхсшитого полистирола, функционализированного третичными аминогруппами, может быть перспективным с точки зрения обеспечения стабильности катализатора при рециклах, однако для достижения 100 % конверсии арилгалогенида (4 - броманизола) требуется применение сильного избытка фенилбороновой кислоты и основания. Катализатор на основе нефункционализированного сверхсшитого полистирола обладает более высокой активностью и позволяет, используя полуторакратный избыток фенилбороновой кислоты, достичь полной конверсии 4 - броманизола за 60 мин реакции в мягких условиях (70 °С, растворитель - смесь этанола и воды в соотношении 5:1). Недостатком такой системы является сильная адсорбция продукта кросс-сочетания в гидрофобной полимерной матрице. This work is devoted to the study of the influence of the type of polymeric matrix of hyper-crosslinked polystyrene on activity and stability of palladium catalysts of Suzuki cross-coupling. The use of the hyper-crosslinked polystyrene functionalized with tertiary amino groups was shown to be promising in terms of ensuring of the catalyst stability during recycles, but in order to achieve 100 % conversion of aryl halide (4 - bromanisole) the use of strong excess of phenylboronic acid and of a base is required. The catalyst based on non-functionalized hyper-crosslinked polystyrene had higher activity and allowed achieving complete conversion of 4 - bromanisole during the reaction under mild conditions (70 °C, ethanol and water mixture is in the ratio of 5 : 1 as a solvent) while using 1,5 - fold excess of phenylboronic acid. However, strong adsorption of the cross-coupling product in a hydrophobic polymeric matrix was found to be a disadvantage of such a system.

Lewis Acid-Promoted Suzuki Reaction using Palladium Chloride Anchored on a Polymer as a Catalyst

2008 ◽  
Vol 61 (8) ◽  
pp. 610 ◽  
Author(s):  
Guozhi Fan ◽  
Hanjun Zhang ◽  
Siqing Cheng ◽  
Zhandong Ren ◽  
Zhijun Hu ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Lewis Acid ◽  
Lewis Acids ◽  
Heterogeneous Catalysts ◽  
Suzuki Reaction ◽  
Cross Coupling ◽  
Palladium Chloride ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Recoverable Catalyst

Palladium chloride anchored on polystyrene modified by 5-amino-1,10-phenanthroline was prepared and used as an efficient recoverable catalyst for Suzuki cross-coupling reactions. The heterogeneous catalysts can be easily separated from the reaction mixture and reused for five cycles without significant Pd leaching and loss of catalytic activity. Rate enhancement in the Suzuki reaction by Lewis acids was also studied.

Comparison of the Suzuki cross-coupling reactions of 4,7-dichloroquinoline and 7-chloro-4-iodoquinoline with arylboronic acids using phosphine-free palladium catalysis in water

2004 ◽  
Vol 82 (2) ◽  
pp. 206-214 ◽  
Author(s):  
Richard W Friesen ◽  
Laird A Trimble
Keyword(s):  
Phenylboronic Acid ◽  
Palladium Catalysis ◽  
Suzuki Reaction ◽  
Tetrabutylammonium Bromide ◽  
Cross Coupling ◽  
Palladium Acetate ◽  
Coupling Reactions ◽  
Reaction Conditions ◽  
Arylboronic Acids ◽  
Cross Coupling Reactions

4,7-Dichloroquinoline (1a) and 7-chloro-4-iodoquinoline (1b) undergo Suzuki cross-coupling reactions with arylboronic acids catalyzed by phosphine-free palladium acetate in boiling water. Using phenylboronic acid (2), the reaction of 1a provides 7-chloro-4-phenylquinoline (3) (78%) together with diphenylquinoline (4) (12%), while 1b reacts in a much more regioselective fashion and provides 3 in 98% isolated yield. Although 1b undergoes a more regioselective Suzuki reaction than 1a, additional important observations are that the overall reaction of 1b with 2 is three times slower than 1a and that the reaction occurs in the absence of tetrabutylammonium bromide. Using optimized reaction conditions, a variety of aryl and vinylboronic acids undergo regioselective Suzuki cross-coupling with 1b to provide the products 7, 10, and 11 in good to excellent yield.Key words: palladium, cross-coupling, regioselectivity, quinolines, boronic acids.

Suzuki-Miyaura Cross-Coupling Towards 4-Amino Biphenyl Intermediates

2019 ◽  
Author(s):  
Tomasz Jastrząbek ◽  
Artur Ulikowski ◽  
Rafał Lisiak
Keyword(s):  
Chemical Industry ◽  
Short Communication ◽  
Phenylboronic Acid ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Amino Groups ◽  
Aryl Chlorides ◽  
Cross Coupling Reaction ◽  
Direct Cross

The preparation of biphenyl derivatives bearing amino groups via direct cross-coupling reaction is being widely explored due to its importance for many branches of the chemical industry. One of the necessary components for such a transformation are halogenated arenes. In order to make the process more economical, we focus on inexpensive and easily available aryl chlorides which usually are not considered reagents of choice for catalytic couplings. In the following short communication, we report the results of the coupling of relatively unreactive chloroaniline with a fluorinated phenylboronic acid leading to the corresponding aminobiphenyl.<br>

scholarly journals QuadraPure-Supported Palladium Nanocatalysts for Microwave-Promoted Suzuki Cross-Coupling Reaction under Aerobic Condition

2014 ◽  
Vol 2014 ◽  
pp. 1-7 ◽  
Author(s):  
Kin Hong Liew ◽  
Poh Lee Loh ◽  
Joon Ching Juan ◽  
Mohd Ambar Yarmo ◽  
Rahimi M. Yusop
Keyword(s):  
Catalytic Activity ◽  
Mechanical Stability ◽  
Physical Adsorption ◽  
Phenylboronic Acid ◽  
Reduction Process ◽  
Cross Coupling ◽  
Aerobic Condition ◽  
Significant Loss ◽  
Coupling Reactions ◽  
Palladium Nanocatalysts

Cross-linked resin-captured palladium (XL-QPPd) was readily prepared by simple physical adsorption onto the high loading QuadraPure macroporous resin and a subsequent reduction process. To enhance the mechanical stability, entrapped palladium nanocatalysts were cross-linked with succinyl chloride. Both transmission electron microscopy images and X-ray diffraction analysis revealed that the palladium nanoparticles were well dispersed with diameters ranging in 4–10 nm. The catalyst performed good catalytic activity in microwave-promoted Suzuki cross-coupling reactions in water under aerobic condition with mild condition by using various aryl halides and phenylboronic acid. In addition, the catalyst showed an excellent recyclability without significant loss of catalytic activity.

scholarly journals Polyvinylpyrrolidone - Reduced Graphene Oxide - Pd Nanoparticles as an Efficient Nanocomposite for Catalysis Applications in Cross-Coupling Reactions

2019 ◽  
Vol 14 (3) ◽  
pp. 490
Author(s):  
Hany A. Elazab ◽  
Tamer T. El-Idreesy
Keyword(s):  
Graphene Oxide ◽  
Catalytic Activity ◽  
Reduced Graphene Oxide ◽  
Cross Coupling ◽  
High Catalytic Activity ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Highly Active ◽  
Defect Sites ◽  
Reduced Graphene

This paper reported a scientific approach adopting microwave-assisted synthesis as a synthetic route for preparing highly active palladium nanoparticles stabilized by polyvinylpyrrolidone (Pd/PVP) and supported on reduced Graphene oxide (rGO) as a highly active catalyst used for Suzuki, Heck, and Sonogashira cross coupling reactions with remarkable turnover number (6500) and turnover frequency of 78000 h-1. Pd/PVP nanoparticles supported on reduced Graphene oxide nanosheets (Pd-PVP/rGO) showed an outstanding performance through high catalytic activity towards cross coupling reactions. A simple, reproducible, and reliable method was used to prepare this efficient catalyst using microwave irradiation synthetic conditions. The synthesis approach requires simultaneous reduction of palladium and in the presence of Gaphene oxide (GO) nanosheets using ethylene glycol as a solvent and also as a strong reducing agent. The highly active and recyclable catalyst has so many advantages including the use of mild reaction conditions, short reaction times in an environmentally benign solvent system. Moreover, the prepared catalyst could be recycled for up to five times with nearly the same high catalytic activity. Furthermore, the high catalytic activity and recyclability of the prepared catalyst are due to the strong catalyst-support interaction. The defect sites in the reduced Graphene oxide (rGO) act as nucleation centers that enable anchoring of both Pd/PVP nanoparticles and hence, minimize the possibility of agglomeration which leads to a severe decrease in the catalytic activity. Copyright © 2019 BCREC Group. All rights reserved 

scholarly journals POSSIBILITY OF PECTIN APPLICATION FOR THE DEVELOPMENT OF SUZUKI REACTION CATALYSTS

2020 ◽  
pp. 26-30
Author(s):  
Полина Михайловна Рассказова ◽  
Линда Жановна Никошвили
Keyword(s):  
Catalytic Properties ◽  
Ambient Pressure ◽  
Phenylboronic Acid ◽  
Suzuki Reaction ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Water Mixture ◽  
Batch Mode ◽  
Modified Alumina ◽  
Cross Coupling Reaction

Работа посвящена синтезу Pd-содержащих катализаторов на основе пектина и исследованию их каталитических свойств в реакции кросс-сочетания Сузуки. Была синтезирована серия катализаторов на основе пектина при варьировании способа осаждения металла. Катализаторы были протестированы в реакции кросс-сочетания между 4-броманизолом и фенилбороновой кислотой в периодическом режиме при атмосферном давлении в смеси этанола и воды с использованием NaCO в качестве основания. Показано, что наибольшей активностью обладает катализатор Pd/(пектин-AlO), в ходе приготовления которого палладий наносился на модифицированный пектином оксид алюминия (конверсия 4-броманизола за 3 ч составила 90%). This work is devoted to the synthesis of Pd-containing catalysts based on pectin and study of their catalytic properties in the Suzuki cross-coupling reaction. A series of catalysts based on pectin was synthesized by varying the method of metal deposition. The catalysts were tested in cross-coupling reaction between 4-bromanisole and phenylboronic acid in a batch mode at ambient pressure in ethanol-water mixture using NaCO as a base. It was shown that the catalyst Pd/(pectin-AlO), which was synthesized via deposition of palladium on pectin-modified alumina, revealed highest activity (conversion of 4-bromanisole for 3 h of reaction reached 90%).

scholarly journals Synthesis and Catalytic Activity of Chiral Dicarbene Dipalladium Complexes Incorporating the S-binaphthol Unit

2018 ◽  
Vol 42 (1) ◽  
pp. 54-56
Author(s):  
Guowen Zhang ◽  
Man Chao ◽  
Shuting Wang ◽  
Mengxia Zhu ◽  
Dou Wang ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Phenylboronic Acid ◽  
Suzuki Reaction ◽  
Aryl Halides ◽  
Sterically Hindered

A series of chiral di-N-heterocyclic carbene (NHC) dipalladium complexes, [{PdPyCl2}2(di-NHC)], in which di-NHC represents a di-imidazolylidene, featuring an (S)-3,3′-dimethyl-2,2′-dimethoxy-1,1′-binaphthalene spacer between the carbene units, have been prepared. The influence of ligand size on the catalytic activity of these complexes in the Suzuki reaction of phenylboronic acid with p-bromotoluene has been investigated. The most sterically hindered complex, bearing the di-isopropylphenyl group, showed the greatest catalytic activity, and it is active for various aryl halides with different electronic and steric properties.

Size-controlled PdO/graphene oxides and their reduction products with high catalytic activity

RSC Advances ◽  
2014 ◽  
Vol 4 (56) ◽  
pp. 29563-29570 ◽  
Author(s):  
Jingjing Lin ◽  
Tao Mei ◽  
Meijiao Lv ◽  
Chang'an Zhang ◽  
Zhenfeng Zhao ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Hydrazine Hydrate ◽  
Electrocatalytic Activity ◽  
Suzuki Reaction ◽  
High Catalytic Activity ◽  
Graphene Oxides ◽  
Highly Active ◽  
The Stability ◽  
Size Controlled ◽  
Better Than

Well-dispersed and size-controlled Pd/RGO with highly active catalysts was synthesized through reduction of PdO/GO with hydrazine hydrate and ammonia. The electrocatalytic activity and the stability of the as-prepared Pd/RGO are much better than those of commercial Pd/C catalysts for methanol electrooxidation and the Suzuki reaction.

Palladium nanoparticles encapsulated inside the pores of a metal–organic framework as a highly active catalyst for carbon–carbon cross-coupling

RSC Advances ◽  
2014 ◽  
Vol 4 (97) ◽  
pp. 54487-54493 ◽  
Author(s):  
Ningzhao Shang ◽  
Shutao Gao ◽  
Xin Zhou ◽  
Cheng Feng ◽  
Zhi Wang ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Palladium Nanoparticles ◽  
Active Catalyst ◽  
Metal Organic Framework ◽  
Cross Coupling ◽  
High Catalytic Activity ◽  
Coupling Reactions ◽  
Highly Active ◽  
Metal Organic ◽  
Organic Framework

Palladium nanoparticles were successfully encapsulated in the cages of MIL-101, which exhibited high catalytic activity toward the C–C coupling reactions.

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