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Campbell, Allea ; Alsudairy, Ziad ; Dun, Chaochao ; Akram, Fazli ; Smith-Petty, Kayla ; Ambus, Abrianna , et al.
Abstract: Covalent organic framework (COF)-supported palladium catalysts have garnered enormous attention for cross-coupling reactions. However, the limited linkage types in COF hosts and their suboptimal catalytic performance have hindered their widespread implementation. Herein, we present the first study immobilizing palladium acetate onto a dioxin-linked COF (Pd/COF-318) through a facile solution impregnation approach. By virtue of its permanent porosity, accessible Pd sites arranged in periodic skeletons, and framework robustness, the resultant Pd/COF-318 exhibits exceptionally high activity and broad substrate scope for the Suzuki-Miyaura coupling reaction between aryl bromides and arylboronic acids at room temperature within an hour, rendering it among the most effective Pd/COF catalysts for Suzuki-Miyaura coupling reactions to date. Moreover, Pd/COF-318 demonstrates excellent recyclability, retaining high activity over five cycles without significant deactivation. The leaching test confirms the heterogeneity of the catalyst. This work uncovers the vast potential of dioxin-linked COFs as catalyst supports for highly active, selective, and durable organometallic catalysis.
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Keywords: covalent organic framework (COF) ; dioxin-linked COF ; Pd(II) immobilization ; Suzuki-Miyaura coupling
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Purchased from AmBeed: 24067-17-2 ; 98-80-6 ; 3375-31-3 ; 71597-85-8 ; 4877-80-9 ; 99768-12-4
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CAS No. : | 24067-17-2 |
Formula : | C6H6BNO4 |
M.W : | 166.93 |
SMILES Code : | OB(C1=CC=C([N+]([O-])=O)C=C1)O |
Synonyms : |
4-Nitrobenzeneboronic Acid; p-Nitrophenylboronic Acid; p-nitro-Benzeneboronic Acid
|
MDL No. : | MFCD00161360 |
InChI Key : | NSFJAFZHYOAMHL-UHFFFAOYSA-N |
Pubchem ID : | 2773552 |
GHS Pictogram: | ![]() |
Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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 |
---|---|---|
78% | With potassium phosphate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; at 80℃; for 3h; | (4-Nitrophenyl) boronic acid (1.2 equivalents), tetrakis (TRIPHENYLPHOSPHINE) palladium (0) (0.03 equivalent) and 2. 0M potassium phosphate solution (2.1 equivalents) are added to a solution under nitrogen of methyl 4-BROMOTHIOPHENE-2-CARBOXYLATE in 3.0 ml of degassed DME. The reaction medium is then stirred for 3 hours at 80oC, diluted with ethyl acetate (20 ml), washed with water (2X15 ml), dried over sodium sulphate, filtered and concentrated under reduced pressure. Chromatography of the residue on silica gel (98/2 dichloromethane/methanol) allows 1.94 g of the expected product to be isolated. Yield: 78% H NMR (CDC13) 5 (PPM) : 3.92 (s, 3H), 7.75 (d, 2H), 7.82 (s, 1H), 8.12 (s, 1H), 8.30 (d, 2H) |
78% | With potassium phosphate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 80℃; for 3h; | To a solution of <strong>[62224-16-2]methyl 4-bromothiophen-2-carboxylate</strong> and 1.2 equivalents of (4-nitrophenyl) boronic acid in DME were added 2. [1] equivalents of a 2.0 M solution of potassium phosphate and 0.03 equivalent of tetrakis (triphenylphosphie) palladium (0). After stirring at [80XB0;C] for 3 hours the mixture was concentrated under reduced pressure. The residue was diluted with ethyl acetate, filtered over Celite, washed with water, dried over sodium sulfate, and then concentrated under vacuum. The residue was purified on a silica gel column using 9: [1] cyclohexane: ethyl acetate to yield 1.94 g (78%) of the desired compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With potassium carbonate;trans-benzyl(chloro)-bis(triphenylphosphine)palladium(II); In 1-methyl-pyrrolidin-2-one; at 110℃; for 48.0h; | 2,5-BIS (TRIFLUOROMETHYL) BROMOBENZENE (0.59 G, 2.00 MMOL, 1.00 EQUIV. ), 4- nitrophenylbronic acid (0.334 g, 2. 00 mmol, 1.00 equiv. ), trans- benzyl (chloro) bis (TRIPHENYLPHOSPHINE) PALLADIUM (LL) (0.076 g, 0.10 mmol, 0.05 EQUIV.), K2CO3 1.38 g, 10.00 MMOL, 5.00 equiv. ) and 10 mL dry NMP were charged to a 25 mL round bottom flask. The mixture was thoroughly de- oxygenated by subjecting to vacuum/nitrogen cycle three times, and heated at 110 C for 2 days under nitrogen protection. Usual workup yielded crude product 4'-nitro-2, 5-bis-trifluoromethyl-biphenyl as brown viscous oil (0. 66 g, 1.97 mmol, 99%). H NMR (300 MHz, CDCl3), 6 (ppm): 8.32 (d, J = 8.7 Hz, 2H); 7. 82-8. 00 (m, 2H); 7.52-7. 61 (m, 3H).The crude product made in the last step was dissolved in 10 mL methylene chloride and 10 mL ethanol. Tin (II) CHLORIDE (2.28 g, 12.00 mmol, 6.00 equiv) was added, followed by addition of 1 mL water. After stirring at room temperature for 2 days, the mixture was neutralized with 2 N NAOH solution, and subjected to usual workup to yield crude product 4'-amino-2, 5-bis-trifluoromethyl- biphenyl (0.52 g, 1.70 mmol, 85% crude yield) as brown viscous oil.4'-Amino-2, 5-bis-trifluoromethyl-biphenyl (0.16 g, 0.50 mmol, 1.00 equiv) was dissolved in 10 mL methylene chloride. To the solution was added 2,3- DIFLUOROBENZOYL chloride (0. 088 g, 0.50 mmol, 1.00 equiv), and triethylamine (0.061 g, 0.60 mmol, 1.20 equiv). The mixture was stirred at room temperature for one hour, and loaded to column for flash chromatography. The title compound was isolated as light yellow solid (0.12 g, 0.27 mmol, 54%). 1H NMR (300 MHz, CDCI3), 6 (PPM) : 8. 39 (D, J= 10.5 Hz, 1H) ; 7.75-7. 95 (m, 6H); 7.63 (s, 1H); 7.26-7. 443 (m, 3H); ESMS CALCD. FOR C21H12F8NO (M + H) + : 446.0 ; Found: 446.0 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,2-dimethoxyethane; water; at 120℃;Microwave irradiation; | Compound 296; N-hydroxy-7-(N-(4-(2-methyl-1H-indol-5-yl)phenyl)methylsulfonamido)heptanamide; As shown in reaction scheme 4,6-bromo-2-methyl-1H-indole and 4-nitrophenylboronic acid were subjected to the Suzuki reaction to obtain compound 2, which was then reduced with palladium/activated carbon to obtain compound 3. Then, compound 3 is allowed to react with ethyl 7-bromoheptanoate to obtain compound 4, which was then allowed to react with methanesulfonyl chloride to obtain a compound of formula V-1, after which the compound of formula V-1 (16 mg, 0.035 mmol) was stirred with hydroxylamine and potassium hydroxide for 30 minutes. Then, a 50percent water solution of hydroxylamine was added to the stirred solution until the undissolved solids were dissolved so that the solution became clear. Then, the reaction solution was stirred at mom temperature for 10 hours, and after the completion of the reaction has been confirmed, the reaction product was concentrated under reduced pressure to remove the solvent. The remaining material was extracted using ethyl acetate, washed with brine, dried with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was crystallized, thus obtaining compound 296 (12 mg, 77.3percent).1H NMR (400 MHz, CD3OD) delta 7.67 (d, J=1.9 Hz, 2H), 7.65 (s, 1H), 7.41 (d, J=6.6 Hz, 2H), 7.30 (d, J=3.5 Hz, 2H), 6.17 (s, 1H), 3.71 (t, J=6.7 Hz, 2H), 2.93 (s, 3H), 2.42 (s, 3H), 2.05 (t, J=7.3 Hz, 2H), 1.57 (m, 4H), 1.31 (m, 4H). MS (ESI) m/z 443 (M++H). | |
(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,2-dimethoxyethane; water; at 120℃;Microwave; | As shown in reaction scheme 4, 6-bromo-2-methyl-1H-indole and 4-nitrophenylboronic acid were subjected to the Suzuki reaction to obtain compound 2, which was then reduced with palladium/activated carbon to obtain compound 3. Then, compound 3 is allowed to react with ethyl 7-bromoheptanoate to obtain compound 4, which was then allowed to react with methanesulfonyl chloride to obtain a compound of formula V-1, after which the compound of formula V-1 (16 mg 0.035 mmol) was stirred with hydroxylamine and potassium hydroxide for 30 minutes. Then, a 50percent water solution of hydroxylamine was added to the stirred solution until the undissolved solids were dissolved so that the solution became clear. Then, the reaction solution was stirred at room temperature for 10 hours, and after the completion of the reaction has been confirmed, the reaction product was concentrated under reduced pressure to remove the solvent. The remaining material was extracted using ethyl acetate, washed with brine, dried with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was crystallized, thus obtaining compound 296 (12 mg, 77.3percent). 1H NMR (400 MHz, CD3OD) delta 7.67 (d, J = 1.9 Hz, 2H), 7.65 (s, 1H), 7.41 (d, J = 6.6 Hz, 2H), 7.30 (d, J = 3.5 Hz, 2H), 6.17 (s, 1H), 3.71 (t, J = 6.7 Hz, 2H), 2.93 (s, 3H), 2.42 (s, 3H), 2.05 (t, J = 7.3 Hz, 2H), 1.57 (m, 4H), 1.31 (m, 4H). MS (ESI) m/z 443 (M+ + H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With tetrakis(triphenylphosphine) palladium(0); caesium carbonate; In 1,4-dioxane; water;Inert atmosphere; Reflux; | General procedure: To a solution of 2,7-dibromonaphthalene (300 mg, 1.05 mmol) in1,4-dioxane (10 mL) were added 4-nitrophenylboronic acid (381 mg, 2.28 mmol), Pd(PPh3)4 (28 mg, 0.024 mmol), and aq. Cs2CO3 (2 M, 2 mL), and the reaction mixture was stirred overnight at reflux under Ar. Then, the reaction mixture was diluted with water (30 mL), and the product was extracted with chloroform (100 mL × 3). The organic layer was dried over MgSO4 and concentrated in vacuo. The residue was purified by column chromatography [hexane/chloroform (2:1)] to give 2,7-bis(4-nitrophenyl)naphthalene 3a (326 mg, 0.879 mmol, 84%) as a yellow solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With bis-triphenylphosphine-palladium(II) chloride; potassium carbonate; In 1,2-dimethoxyethane; water; at 120℃; for 1h;Microwave irradiation; Inert atmosphere; | <strong>[57876-69-4]2-chloro-3-methylquinoline</strong> (1 .00 g, 5.65 mmol), (4-nitrophenyl)boronic acid (1 .20 g, 7.22 mmol), and Pd(PPh3)2C12 catalyst (19.7 mg) was added to DME (16 mL)in a microwave vial. 2M aqueous potassium carbonate was added (4 mL) added, vial capped and then mix degassed with nitrogen before being irradiated in the microwave at 120C for 1 hour. The reaction mixture was partitioned between ethyl acetate and sat. aqueous sodium bicarbonate solution. Organic phase was washed with water, dried (Mg504) and concentrated to give a light tan solid, which was purified by flash chromatography on silica gel (40g), eluting with a gradient of 20-50% EtOAc in hexane to give a light-cream solid (1.32 g, 88%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With copper(I) 2-hydroxy-3-methylbenzoate; potassium carbonate; In methanol; at 65℃; for 3h; | General procedure: A dry flask was charged with the nitrogen containing heterocycles (1 mmol), aryl boronic acids (2.2 mmol), potassium carbonate (2 mmol) andCuMeSal (0.015 mmol)then anhydrous methanol (10 ml) was added. The reaction mixture was stirred at 65 oC, open to air, for 3 h (5 h in case of indole and benzimidazole), cooled to room temperature, filtered, and the precipitate was washed with methanol (2 ml), the filtrate was concentrated under vacuum, then stirred with ice water (30 ml) and extracted with ethyl acetate (3 × 50 ml), dried over sodium sulfate and the solvent was removed under reduced pressure. The residue was purified by chromatography or recrystallization as indicated with each compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With copper(l) iodide; sulfur; sodium t-butanolate; at 60 - 80℃; for 10h; | General procedure: A one-necked flask was charged with CuI (30 mg, 0.15 mmol), NaOt-Bu (376 mg, 4.0 mmol), S8 (47 mg, 1.5 mmol), phenolic ester (1 mmol), arylboronic acid (1.1 mmol), and PEG200 (2 mL). The mixture was magnetically stirred and heated at 60-80 C for the appropriate reaction time (Table 2). After completion of the reaction, the reaction mixture was cooled to r.t. H2O (4 mL) was added and the product was extracted with EtOAc (3 × 4 mL) and dried (anhyd Na2SO4). Evaporation of the solvent and purification by column chromatography on silicagel (n-hexane/EtOAc) gave the desired unsymmetrical diaryl sulfides in 74-95% yields. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95.4% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate; In 1,4-dioxane; water; at 80℃; | To a solution of <strong>[858629-06-8]5-fluoro-3-iodo-1H-indazole</strong> (2.0 g, 7.6 mmol) in dioxane (40 mL) and H20 (10 mL) was added 4-nitrophenylboronic acid (1.89 g, 11.4 mmol) and K2C03 (2.09 g, 15.2 mmol), Pd(dppf)C12 (555.56 mg, 0.76 mmol), the mixture was stirred at 80 C overnight. The reaction was monitored by TLC. After completion, the mixture was filtered, the filtrate was concentrated in vacuum to give a residue, which was purified by a silica gel column (PE/EA = 3/1) to afford 5-fluoro-3-(4-nitro-phenyl)-1H-indazole (1.87 g, yield: 95.4%) as a yellow solid. ‘HNIVIR (400 IVIHz, DMSO-d6): ö = 14.06 (s, 1H), 8.41-8.28 (m, 4H), 7.99 (dd,J 7.2, 2.0 Hz, 1H), 7.73 (dd, J 4.4, 4.8 Hz, 1H), 7.41-7.33 (m, 1H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56.00% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate; In 1,4-dioxane; water; toluene; at 80℃; for 12h;Inert atmosphere; | A mixture of 4-nitrophenyl)boronic acid (23.00 g, 137.78 mmol, 1.00 eq.), 2-bromothiazole (25.54 g, 155.69 mmol, 14.03 mL, 1.13 eq.), Na2C03 (36.51 g, 344.45 mmol, 2.50 eq.) and Pd(dppf)Cl2.CH2Cl2 (6.75 g, 8.27 mmol, 0.06 eq.) in Tol. (250.00 mL)/H20 (100.00 mL)/dioxane (250.00 mL) was degassed and purged with N2 for 3 times. The mixture was stirred at 80C for 12 hrs under N2 atmosphere and LCMS showed the reaction was complete. The mixture was concentrated and the residue was purified by column chromatography (Petroleum ethenEthyl acetate=50: l to 5: 1) to give 2-(4-nitrophenyl)thiazole (14.00 g, 67.89 mmol, 56.00% yield) as a yellow solid. 1H NMR (400MHz, CHLOROFORM-d) delta = 8.35 - 8.29 (m, 2H), 8.21 - 8.12 (m, 2H), 7.99 (d, J = 3.2 Hz, 1H), 7.50 (d, J = 3.2 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69.5% | With palladium diacetate; potassium carbonate; triphenylphosphine; In water; N,N-dimethyl-formamide; at 100℃; for 3h;Inert atmosphere; Microwave irradiation; Sealed tube; | <strong>[16870-28-3]2-hydroxy-4-iodobenzoic acid</strong> (50 mg, 0.189 mmol), 4-nitrobenzeneboronic acid (38 mg, 0.227 mmol), PPh3 (7.4 mg, 0.028 mmol), K2CO3 (91.4 mg, 0.662 mmol), Pd(AcO)2 (2.12 mg, 0.0095 mmol), 1:1 DMF: H2O (2 ml) were used. In this case, prior to chromatographic purification, the residue from evaporating the filtrate was resuspended in acetonitrile. The precipitate was separated from the liquid phase and the latter was discarded. The solid was then purified by flash chromatography (elution with AcOEt: CH3CN:H2O:CH3OH 70:10:5:5 mixture). Compound 101 was obtained as a yellowish solid. Yield after purification: 69.5 % (34 mg). 1H NMR (500 MHz, methanol-d4) delta 8.31 (d, J = 8.9 Hz, 2H), 7.96 (d, J = 7.94 Hz, 1H), 7.87 (d, J = 8.9 Hz, 2H), 7.17-7.13 (m, 2H). 13C NMR (126 MHz, methanol-d4) delta 175.2 (CO), 163.1 (C), 148.7 (C), 148.2 (C), 144.5 (C), 132.4 (CH), 129.1 (2CH), 124.9 (2CH), 119.5 (C), 118.1 (CH), 116.1 (CH). HRMS (TOF, ES-): Calculated for C13HsNO5: (M-H)-: m/z 258.0402. 258.0411 found (deviation 3.5 ppm). m.p. (C) > 300 |
Tags: 4-Nitrophenylboronic acid | Benzene Compounds | Organoboron | Boronic Acids | Aryls | Nitroes | Organometallic Reagents | Boronic Acids/Esters | Organic Building Blocks | 24067-17-2
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H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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