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.

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 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 INFLUENCE OF METAL-MODIFIERS ON THE BEHAVIOR OF LIGANDLESS PALLADIUM CATALYSTS OF SUZUKI CROSS-COUPLING

2020 ◽  
pp. 18-25
Author(s):  
Линда Жановна Никошвили ◽  
Кристина Николаевна Шкерина ◽  
Елизавета Евгеньевна Пономарчук ◽  
Михаил Геннадьевич Сульман
Keyword(s):  
Palladium Catalysts ◽  
Phase Transfer ◽  
Phenylboronic Acid ◽  
Cross Coupling ◽  
Solvent Mixture ◽  
Amino Groups ◽  
Batch Mode ◽  
Hydrogen Flow ◽  
Crosslinked Polystyrene ◽  
Tertiary Amino

В работе рассмотрены перспективы введения второго металла-модификатора в состав палладий-содержащих катализаторов кросс-сочетания Сузуки. Представлены результаты проверки каталитических свойств моно- (Pd) и биметаллических (Au-Pd, Pd-Cu, Pd-Zn) безлигандных катализаторов на основе сверхсшитого полистирола марки MN100, содержащего третичные аминогруппы, в модельной реакции кросс-сочетания 4-броманизола и фенилбороновой кислоты. Реакция проводилась на воздухе в периодическом режиме в мягких условиях (растворитель - смесь этанола и воды в объемном соотношении 4 : 1, температура 60С, основание - NaOH) в отсутствии агентов фазового переноса. Было показано, что в случае образца Pd/MN100, предварительно восстановленного в токе водорода, для достижения 100% конверсии 4-броманизола за 60 мин важно обеспечить определенный избыток фенилбороновой кислоты и NaOH (селективность по продукту кросс-сочетания при этом сохраняется равной 89%). Среди биметаллических образцов наибольшей активностью обладал катализатор Au-Pd/MN100 (достигалась 100% конверсия 4-броманизола за 15 мин реакции), однако наиболее селективным был образец Pd-Cu/MN100 (селективность составила 93%). This paper is devoted to the prospects of introducing the second metal-modifier into the composition of palladium-containing catalysts of Suzuki cross-coupling. The results of catalytic testing of mono- (Pd) and bimetallic (Au-Pd, Pd-Cu, Pd-Zn) ligandless catalysts based on hyper-crosslinked polystyrene of MN100 type containing tertiary amino-groups in the model reaction of cross-coupling of 4-bromanisole and phenylboronic acid are presented. The reaction was carried out in air in a batch mode under mild conditions (solvent - mixture of ethanol and water in a volumetric ratio of 4 : 1, temperature 60C, NaOH was used as a base) in the absence of phase-transfer agents. It was shown that in the case of Pd/MN100 sample preliminarily reduced in hydrogen flow, it is important to provide a certain excess of phenylboronic acid and NaOH in order to achieve 100% conversion of 4-bromanisole in 60 min (selectivity with respect to cross-coupling product was maintained at 89%). Among bimetallic samples, the catalyst Au-Pd/MN100 revealed the highest activity (100% conversion of 4-bromanisole was achieved in 15 min of reaction), however Pd-Cu/MN100 sample was the most selective (selectivity was 93%).

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.

Palladium-catalyzed heck and suzuki coupling in glycerol

2007 ◽  
Vol 61 (3) ◽  
Author(s):  
A. Wolfson ◽  
C. Dlugy
Keyword(s):  
Diethyl Ether ◽  
Palladium Catalysts ◽  
Phenylboronic Acid ◽  
Cross Coupling ◽  
Palladium Complexes ◽  
Organic Substrates ◽  
Heck Coupling ◽  
Green Solvent ◽  
Palladium Catalyzed ◽  
Simple Extraction

AbstractThe Heck coupling of halobenzenes with various alkenes and the Suzuki cross coupling of halobenzenes with phenylboronic acid were successfully performed in glycerol as the reaction solvent using homogeneous and heterogeneous palladium catalysts. Glycerol is a renewable and recyclable green solvent that is able to dissolve organic substrates, inorganic bases, and palladium complexes, and that allows easy isolation of the reaction product by simple extraction with glycerol-immiscible solvents such as diethyl ether, hexane, and dichloromethane.

Highly active organosilane-based N-heterocyclic carbene-palladium complex immobilized on silica particles for the Suzuki reaction

2007 ◽  
Vol 79 (9) ◽  
pp. 1553-1559 ◽  
Author(s):  
Sang-Myung Lee ◽  
Hyo-Jin Yoon ◽  
Jong-Ho Kim ◽  
Woo-Jae Chung ◽  
Yoon-Sik Lee
Keyword(s):  
Electron Microscopy ◽  
Catalytic Activity ◽  
Inductively Coupled Plasma ◽  
Aryl Halide ◽  
Phenylboronic Acid ◽  
Suzuki Reaction ◽  
Atomic Emission ◽  
Silica Particles ◽  
Significant Loss ◽  
Imidazolium Chloride

1-Methyl-3-(3-trimethoxysilylpropyl)imidazolium chloride, [TMSPIM][Cl-], was synthesized as a precursor of N-heterocyclic carbene (NHC), which can be coordinated with palladium to give an organosilane-based bidentic NHC-Pd complex. The organosilane-based NHC-Pd complex was immobilized covalently on silica particles (NHC-Pd/silica) and then characterized by field emission/scanning electron microscopy (FE/SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIRS), and inductively coupled plasma/atomic emission spectroscopy (ICP/AES). The Suzuki reaction was performed as a model reaction to examine the catalytic activity of NHC-Pd/silica. NHC-Pd/silica exhibited excellent performance in the Suzuki reaction of various aryl halide derivatives (except for aryl chloride derivatives) with phenylboronic acid under mild conditions (room temperature and short reaction time). Moreover, the catalyst was recycled several times without any significant loss of catalytic activity in the Suzuki reaction.

scholarly journals Pd Nanoparticles Stabilized by Hypercrosslinked Polystyrene Catalyze Selective Triple C-C Bond Hydrogenation and Suzuki Cross-Coupling

2019 ◽  
Vol 2019 ◽  
pp. 1-7 ◽  
Author(s):  
Linda Zh. Nikoshvili ◽  
Nadezhda A. Nemygina ◽  
Tatiana E. Khudyakova ◽  
Irina Yu. Tiamina ◽  
Alexey V. Bykov ◽  
...  
Keyword(s):  
Phase Transfer ◽  
Aryl Halide ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Pd Nanoparticles ◽  
Hypercrosslinked Polystyrene ◽  
Reductive Activation ◽  
Pd Nanoparticle ◽  
Cross Coupling Reaction ◽  
Precursor Decomposition

This paper describes the synthesis of Pd-containing catalysts based on nonfunctionalized hypercrosslinked polystyrene via impregnation with Pd acetate. Developed Pd nanoparticulate catalyst allowed achieving conversion of aryl halide up to 90% in Suzuki cross-coupling reaction under mild conditions and at the absence of phase-transfer agents. During the selective hydrogenation of triple C-C bond of 2-methyl-3-butyn-2-ol, up to 96% selectivity with respect to corresponding olefinic alcohol was found at 95% conversion. The influences of the procedure of catalyst synthesis like precursor decomposition and reductive activation method on Pd nanoparticle formation are discussed.

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.

scholarly journals Flow Process Development and Optimization of A Suzuki-Miyaura Cross Coupling Reaction using Response Surface Methodology

2020 ◽  
Vol 15 (3) ◽  
pp. 604-616
Author(s):  
Girish Basavaraju ◽  
Ravishankar Rajanna
Keyword(s):  
Response Surface Methodology ◽  
Response Surface ◽  
Flow Reactor ◽  
Phenylboronic Acid ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Flow Process ◽  
Cross Coupling Reaction ◽  
Custom Made ◽  
Good Agreement

A custom-made tubular flow reactor was utilized to develop a mathematical model and optimize the Suzuki-Miyaura cross coupling reaction. In this study, the experimentation was designed and executed through the statistical design of experiments (DoE) approach via response surface methodology. The effect of molar ratios of phenylboronic acid (1) and 4-bromophenol (2), temperature, the catalyst tetrakis(triphenylphosphine)palladium, and equivalence of aqueous tripotassium phosphate was studied in detail. The flow reactor profile was in good agreement with batch conditions and significant improvements to the overall reaction time and selectivity towards desired [1-1-biphenyl]-4-ol (3) was achieved. The Suzuki coupling reaction in batch condition would take on an average of 4 to 6 hours to complete, which was effectively accomplished in 60 to 70 minutes in this tubular reactor setup and could be operated continuously. The reaction model is in good agreement with the reaction conditions. Copyright © 2020 BCREC Group. All rights reserved 

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