Acceleration of Batch-type Heterogeneous Ligand-free Suzuki-Miyaura Reactions with Polymer Composite Supported Pd Catalyst
Abstract An efficient and recyclable palladium (II) catalyst supported on a double-structured amphiphilic polymer composite was reported previously containing a polymer hydrogel within macroporous polystyrene (PS) microspheres. However, some critical questions have been unaddressed. First, the catal...
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2017
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oai:doaj.org-article:c9a9a382d43e4924b3b813e10cf1d7d12021-12-02T16:06:28ZAcceleration of Batch-type Heterogeneous Ligand-free Suzuki-Miyaura Reactions with Polymer Composite Supported Pd Catalyst10.1038/s41598-017-06499-z2045-2322https://doaj.org/article/c9a9a382d43e4924b3b813e10cf1d7d12017-08-01T00:00:00Zhttps://doi.org/10.1038/s41598-017-06499-zhttps://doaj.org/toc/2045-2322Abstract An efficient and recyclable palladium (II) catalyst supported on a double-structured amphiphilic polymer composite was reported previously containing a polymer hydrogel within macroporous polystyrene (PS) microspheres. However, some critical questions have been unaddressed. First, the catalyst accelerated the heterogeneous ligand-free batch Suzuki-Miyaura reaction in a H2O/EtOH mixture solution at room temperature in the presence of air, which could be ascribed to the “on-water” effect taking place at the interface of the aqueous–organic and basic-aqueous phases created by sodium carbonate in H2O/EtOH. To this acceleration, the double-structured amphiphilic polymer composite can also contribute by providing hydrogels inside the macroporous PS that served as a microreactor. This microreactor allowed the reactions to quickly proceed across the two immiscible (i.e. aqueous-organic and basic-aqueous) phases. Moreover, hydrogels containing hydroxyl groups can also serve as phase-transfer catalysts (PTC) to promote the Suzuki reaction. Second, the deactivated catalyst recovered its initial catalytic activity after overnight air exposure. This observation indicates the importance of oxygen in the activation/deactivation of Pd metals, as determined by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) measurements which revealed different Pd oxidation states with various morphologies before and after Suzuki reactions.Mian WangHan XueFei JuHaijie YangNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 7, Iss 1, Pp 1-9 (2017) |
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Medicine R Science Q Mian Wang Han Xue Fei Ju Haijie Yang Acceleration of Batch-type Heterogeneous Ligand-free Suzuki-Miyaura Reactions with Polymer Composite Supported Pd Catalyst |
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Abstract An efficient and recyclable palladium (II) catalyst supported on a double-structured amphiphilic polymer composite was reported previously containing a polymer hydrogel within macroporous polystyrene (PS) microspheres. However, some critical questions have been unaddressed. First, the catalyst accelerated the heterogeneous ligand-free batch Suzuki-Miyaura reaction in a H2O/EtOH mixture solution at room temperature in the presence of air, which could be ascribed to the “on-water” effect taking place at the interface of the aqueous–organic and basic-aqueous phases created by sodium carbonate in H2O/EtOH. To this acceleration, the double-structured amphiphilic polymer composite can also contribute by providing hydrogels inside the macroporous PS that served as a microreactor. This microreactor allowed the reactions to quickly proceed across the two immiscible (i.e. aqueous-organic and basic-aqueous) phases. Moreover, hydrogels containing hydroxyl groups can also serve as phase-transfer catalysts (PTC) to promote the Suzuki reaction. Second, the deactivated catalyst recovered its initial catalytic activity after overnight air exposure. This observation indicates the importance of oxygen in the activation/deactivation of Pd metals, as determined by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) measurements which revealed different Pd oxidation states with various morphologies before and after Suzuki reactions. |
format |
article |
author |
Mian Wang Han Xue Fei Ju Haijie Yang |
author_facet |
Mian Wang Han Xue Fei Ju Haijie Yang |
author_sort |
Mian Wang |
title |
Acceleration of Batch-type Heterogeneous Ligand-free Suzuki-Miyaura Reactions with Polymer Composite Supported Pd Catalyst |
title_short |
Acceleration of Batch-type Heterogeneous Ligand-free Suzuki-Miyaura Reactions with Polymer Composite Supported Pd Catalyst |
title_full |
Acceleration of Batch-type Heterogeneous Ligand-free Suzuki-Miyaura Reactions with Polymer Composite Supported Pd Catalyst |
title_fullStr |
Acceleration of Batch-type Heterogeneous Ligand-free Suzuki-Miyaura Reactions with Polymer Composite Supported Pd Catalyst |
title_full_unstemmed |
Acceleration of Batch-type Heterogeneous Ligand-free Suzuki-Miyaura Reactions with Polymer Composite Supported Pd Catalyst |
title_sort |
acceleration of batch-type heterogeneous ligand-free suzuki-miyaura reactions with polymer composite supported pd catalyst |
publisher |
Nature Portfolio |
publishDate |
2017 |
url |
https://doaj.org/article/c9a9a382d43e4924b3b813e10cf1d7d1 |
work_keys_str_mv |
AT mianwang accelerationofbatchtypeheterogeneousligandfreesuzukimiyaurareactionswithpolymercompositesupportedpdcatalyst AT hanxue accelerationofbatchtypeheterogeneousligandfreesuzukimiyaurareactionswithpolymercompositesupportedpdcatalyst AT feiju accelerationofbatchtypeheterogeneousligandfreesuzukimiyaurareactionswithpolymercompositesupportedpdcatalyst AT haijieyang accelerationofbatchtypeheterogeneousligandfreesuzukimiyaurareactionswithpolymercompositesupportedpdcatalyst |
_version_ |
1718384989275422720 |