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Guo, Sheng ; Wu, Yifan ; Luo, Shao-Xiong Lennon , et al. ACS Appl. Nano Mater.,2022,5(12):18603-18611. DOI: 10.1021/acsanm.2c04393
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Abstract: Heterogenous catalysts with confined nanoporous catalytic sites are shown to have high activity and size selectivity. A solution-processable nanoporous organic polymer (1-BPy-Pd) catalyst displays high catalytic performance (TON > 200K) in the heterogeneous Suzuki–Miyaura coupling (SMC) reaction and can be used for the preparation of the intermediates in the synthesis of pharmaceutical agents. In comparison to the homogeneous catalyst analogue (2,2′-BPy)PdCl2, the heterogenous system offers size-dependent catalytic activity when bulkier substrates are used. Furthermore, the catalyst can be used to create catalytic impellers that simplify its use and recovery. We found that this system also works for applications in heterogenous Heck and nitroarenes reduction reactions. The metal-binding nanoporous polymer reported here represents a versatile platform for size-selective heterogeneous and recyclable catalysts.
Keywords: nanoporous organic polymer ; heterogeneous catalyst ; Suzuki?Miyaura coupling reaction ; size-selective reaction ; catalyst processing
Purchased from AmBeed: 128796-39-4 ; 10365-98-7 ; 98-80-6 ; 556-96-7 ; 171663-13-1 ; 71597-85-8 ; 402-43-7 ; 2042-37-7 ; 22385-77-9 ; 16419-60-6 ; 15862-18-7 ; 87199-15-3 ; 171408-84-7 ; 643-58-3 ; 591-50-4 ; 76911-73-4 ; 398-36-7 ; 14871-92-2 ; 5720-07-0 ; 945976-76-1 ; 366-18-7 ; 2920-38-9 ; 623-00-7 ; 24973-49-7 ; 588-59-0 ; 128796-39-4 ; 5723-93-3 ; 17057-88-4 ; 126485-55-0 ...More
CAS No. : | 87199-15-3 | MDL No. : | MFCD01317846 |
Formula : | C7H9BO3 | Boiling Point : | - |
Linear Structure Formula : | OHCH2C6H4B(OH)2 | InChI Key : | HGTDLKXUWVKLQX-UHFFFAOYSA-N |
M.W : | 151.96 | Pubchem ID : | 2734662 |
Synonyms : |
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Chemical Name : | 3-(Hydroxymethyl)phenylboronic acid |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With C44H32Cl4I2N4P2Pd2; tetrabutylammomium bromide; caesium carbonate; In water; at 100℃; for 12h;Inert atmosphere; | General procedure: A Schlenk tube was charged with the prescribed amount of catalyst, aryl halide (1.0 mmol), 3-(hydroxymethyl)phenylboronicacid (1.5 mmol), TBAB (1.0 mmol), the selected base (3.0 mmol), and water under nitrogen atmosphere. The reaction mixture was heated at 100 C for 12 h. After cooling,the mixture was extracted with CH2Cl2, the solvent was evaporated,and the product was separated by passing through a silica gel column with CH2Cl2/ethyl acetate (5:1) aseluent. The products 2f, 2j, 2l, and 2o were new compounds and were determined by 1H and C13 NMR. Other products were characterized by comparison with data in the literature. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51.4% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate; In 1,4-dioxane; water; at 110℃; for 2h;Inert atmosphere; | To a solution of methyl 6-chloro-3-methyl-pyridine-2- carboxylate (1.0 g, 5.39 mmol) in 1,4-dioxane (17.9 ml) and H20 (2.9 ml) is added (3- (hydroxymethyl)phenyl)boronic acid (0.982 g, 6.47 mmol) followed by K2C03 (1.86 g, 13.47 mmol) and PdCl2(dppf)*CH2Cl2 (131.9 mg, 0.13 mmol). The reaction mixture is purged with argon for 5 minutes and then heated at 110C. After 2 hours, the reaction is cooled to room temperature, diluted with water and extracted with EtOAc. The combined organic layers are dried over magnesium sulfate, filtered, and concentrated. The residue is purified by silica gel flash chromatography using 70% EtOAc in hexane to afford methyl 6-[3-(hydroxymethyl)phenyl]-3-metliyl-pyridine-2-carboxylate (0.713 g, 51.4%). Mass spectrum (m/z): 258.0 (M+l)+. |
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