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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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Qiao Lin ; Ethan H. Spielvogel ; Tianning Diao ;
Abstract: The capture of carbon-centered radicals at a nickel(II) center is commonly featured in recent cross-coupling and metallaphotoredox catalytic reactions. Despite its widespread application in catalysis, this fundamental step lacks experimental characterization. This report portrays radical capture at catalytically relevant nickel(II) centers from several aspects, including the structure-activity relationships of the ligands, the mechanism, the kinetics, and the stereoselectivity. Spectroscopic data provide evidence for the formation of a nickel(III) intermediate. Strikingly different reactivity between nickel-aryl and nickel-alkyl complexes implies different rate-determining steps for C(sp3)–C(sp3) and C(sp2)–C(sp3) bond formation. Kinetic data benchmark the capture rates on the scale of 10[7] M−1s−1 and 10[6] M−1s−1 for primary and secondary radicals, respectively. Overall, the activation energy is higher than that of previous computational estimations. Finally, stoichiometric experiments with well-defined chiral nickel complexes demonstrate that the radical trapping step can confer diastereoselectivity and enantioselectivity with a drastic ligand effect.
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Purchased from AmBeed: 142946-79-0 ; 50487-71-3 ; 3395-91-3 ; 22980-76-3 ; 2706576-80-7 ; 119165-69-4 ; 402-43-7 ; 27060-75-9 ; 6346-09-4 ; 117408-98-7 ; 957034-45-6 ; 7318-00-5 ; 403-39-4 ; 366-18-7 ; 401-79-6 ; 929000-62-4 ; 459-47-2 ; 1416819-91-4 ; 605-39-0 ; 44565-27-7 ; 10285-80-0 ; 458-76-4 ; 5789-35-5 ; 1165-06-6 ; 1595706-68-5 ; 27820-98-0
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Guo, Sheng ; Wu, Yifan ; Luo, Shao-Xiong Lennon ; Swager, Timothy M. ;
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.
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Keywords: nanoporous organic polymer ; heterogeneous catalyst ; Suzuki−Miyaura coupling reaction ; size-selective reaction ; catalyst processing
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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
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CAS No. : | 402-43-7 |
Formula : | C7H4BrF3 |
M.W : | 225.01 |
SMILES Code : | FC(C1=CC=C(Br)C=C1)(F)F |
MDL No. : | MFCD00000398 |
InChI Key : | XLQSXGGDTHANLN-UHFFFAOYSA-N |
Pubchem ID : | 67872 |
GHS Pictogram: |
![]() ![]() |
Signal Word: | Danger |
Hazard Statements: | H225-H315-H319 |
Precautionary Statements: | P210-P233-P240-P241-P242-P243-P264-P280-P303+P361+P353-P305+P351+P338-P332+P313-P337+P313-P370+P378-P403+P235-P501 |
Class: | 3 |
UN#: | 1993 |
Packing Group: | Ⅲ |
* 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 |
---|---|---|
With caesium carbonate;PdCl2[dppf]; In tetrahydrofuran; N,N-dimethyl-formamide; | Step 4. Preparation of (4'-Trifluoromethyl-biphenyl-4-yl)-methanol (compound 36D) 1-Bromo-4-trifluoromethyl-benzene (814 mg, 3.62 mmol), 4-hydroxymethylphenylboronic acid (600 mg, 3.98 mmol), cesium carbonate (2.36 g, 7.24 mmol), and PdCl2(dppf) (132 mg, 0.181 mmol) were added to 10 ml of a 1:1 solution of DMF/THF. The reaction was flushed with nitrogen and heated to 90 C. for 1 h. The reaction was cooled, poured into diethyl ether and washed with water (2*50 ml), brine (1*50 ml) and dried over anhydrous sodium sulfate. The crude product was filtered through silica gel, eluted with diethyl ether, and concentrated to provide the title compound. MS m/z 251 (M-1). | |
With caesium carbonate;palladium dichloride; In tetrahydrofuran; DMF (N,N-dimethyl-formamide); at 90℃; for 1h;Heating / reflux; | Step 1.Preparation of (4'-Trifluoromethyl-biphenyl-4-yl)-methanol (Compound 3A) 1-Bromo-4-trifluoromethyl-benzene (814 mg, 3.62 mmol), 4-hydroxymethylphenylboronic acid (600 mg, 3.98 mmol), cesium carbonate (2.36 g, 7.24 mmol), and PdCl2(dppf) (132 mg, 0.181 mmol) were added to 10 ml of a 1:1 solution of DMF/THF. The reaction was flushed with nitrogen and heated to 90 C. for 1 h.The reaction was cooled, poured into diethyl ether and washed with water (2*50 ml), brine (1*50 ml) and dried over anhydrous sodium sulfate.The crude product was filtered through silica gel, eluted with diethyl ether, and concentrated to provide the title compound. MS m/z 251 (M-1). | |
With bis-triphenylphosphine-palladium(II) chloride; caesium carbonate; In tetrahydrofuran; N,N-dimethyl-formamide; at 90℃; for 1h;Inert atmosphere; | A mixture of Compound 33A (450 mg, 2.0 mmol), 4- (hydroxymethyl)phenylboronic acid (334 mg, 2.2 mmol), CS2CO3 (1.30 g, 4.0 mmol), and Pd(PPh3)Cl2 (140 mg, 0.2 mmol) in DMF/THF (10 mL, 1 : 1 in volume) was heated at 90 C under nitrogen for 1 hour. The mixture was cooled down to room temperature, diluted with diethyl ether (50 mL), washed with water (50 mL x 2) and brine (50 mL), dried over anhydrous sodium sulfate, filtered, and concentrated to give a crude product, which was purified with column chromatography on silica gel (ethyl acetate in petroleum ether, from 0% to 10% v/v) to yield Compound 33B: LC-MS (ESI) m/z: 235 [M-OH]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | With hydrogenchloride; n-butyllithium; In diethyl ether; hexane; water; | PREPARATION OF TRIS(4-TRIFLUOROMETHYLPHENYL)PHOSPHINE (R=4-trifluomethylphenyl) 8 grams of 4-bromobenzotrifluoride were dissolved in 45 milliliters of anhydrous diethylether at 0° C. under a nitrogen atmosphere. 14 milliliters of a 2.5 M solution of n-butyllithium in hexane were then added to the solution via syringe, with stirring, over a 10 minute period. The solution was stirred for 30 minutes at 0° C., and then a solution of 1 milliliter of phosphorous trichloride in 15 milliliters of diethylether was added to the solution dropwise over a 50 minute period. The resulting mixture was warmed to room temperature and stirred for 21/2 hours, then quenched with 50 milliliters of a 5 percent solution of hydrochloric acid. The organic phase of the mixture was washed with 50 milliliters of water, followed by 50 milliliters of aqueous sodium chloride solution. The organic phase was then dried over magnesium sulfate, filtered, and concentrated on a rotavap (rotary evaporator). The resulting product was a red-orange oil, yield 5.31 grams. The product included a triarylphosphine oxide side-product. The side-product was removed by precipitation by the addition of hexane, followed by filtration of the side product. The hexane solvent was removed on a rotavap, and the final product was an orange oil which crystallized upon standing. The triarylphosphine product was purified by recrystallization from methanol. The final yield of the triarylphosphine product was 1.95 grams (yield 35percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
27% | With potassium carbonate; In dimethyl sulfoxide; | 4-(4-Trifluormethylphenoxy)aniline: To a stirred solution of 4-trifluormethylbromobenzene (11.2 g, 50 mmol) in dimethylsulphoxide (50 mL) is added powdered potassium carbonate (3.4g, 60 mmol) and 4-aAminophenol (6.6 g, 55 mmol). The suspension is heated at 90C for 4.5 h, then poured into water, extracted with di-isopropylether, filtered, decanted, the organic phase washed with water, dried (magnesium sulphate) and evaporated to give 9.6 g of a brown oil. To this triturated with pentane, the resulting precipitate filtered, washed with pentane and dried to give 3.3 g of the title compound (27%, mp. 72 C). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.8 g of Grignard magnesium are placed in 19 ml of anhydrous ethyl ether in a round-bottomed flask equipped with a mechanical stirrer, and under a stream of nitrogen. A mixture of 8.9 ml of 4-bromotrifluoromethylbenzene in 46 ml of anhydrous ethyl ether is then added. The mixture is stirred for one hour, followed by addition of a solution of 5.7 g of <strong>[18711-15-4]4,6-dichloro-1H-indole-2,3-dione</strong> in 100 ml of anhydrous THF. The mixture is stirred at room temperature for 4 hours 30 minutes. Water is added and the resulting mixture is extracted with ethyl acetate. The organic phase is separated out and dried over Na2SO4, filtered and evaporated under vacuum. The residue is taken up in ethyl acetate and washed with 1N sodium hydroxide solution. The organic phase is dried over Na2SO4, filtered and evaporated under vacuum. The solid is taken up in ethyl ether and filtered off. 4.7 g of expected product are obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With caesium carbonate;palladium diacetate; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In 1,4-dioxane; at 20 - 80℃; for 16h; | EXAMPLE 62; (^-{(3ffy2-oxo-l-[4-ftrifluorommethylamino diazen- 1 -ium- 1 ,2-diolate; Step A: (3^-3-hydroxy- 1 -[4-(trifluoromethyl phenyl pyrrolidin-2-one; To a 1,4-dioxane (20 mL) solution of (3S -3-hydroxypyrrolidin-2-one (372 mg, 3.68 mmol) and l-bromo-4-(trifluoromethyl)benzene (508 , 3.68 mmol) at room temperature was added 4s5-bis(diphenylphosphino)-9,9-dirnethylxanthene (64 mg, 0.1 1 mmol), palladium(H) acetate (17 mg, 0.070 mmol) and cesium carbonate (1.80 g, 5.52 mmol), After stirring at 80 °C for 16 hours, the reaction mixture was allowed to cool down to room temperature and partitioned between diethyl ether (100 mL) and brine (100 mL). The organic layer was washed with brine (2 x 100 mL), dried (magnesium sulfate) and concentrated in vacuo to afford the crude product. Chromatography over silica gel, eluting with hexanes/ethyl acetate, afforded the title compound. 1H NMR (500 MHz, CDC ) delta 7.81 (d, J= 8.6 Hz, 2H), 7.64 (d, J= 8.7 Hz, 2H), 4.52-4.48 (m, 1H), 3.89-3.77 (m, 2H), 3.05 (br s, 1H), 2.68-2.62 (m, 1H), 2.18-2.09 (m, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | With PdCl(C3H5)(dppb); potassium acetate; In N,N-dimethyl acetamide; at 120℃; for 20h;Inert atmosphere; | 4-(Trifluoromethyl)bromobenzene (0.225 g, 1 mmol), <strong>[100063-22-7]methyl 3-amino-5-phenylthiophene-2-carboxylate</strong> (0.466 g, 2 mmol) and KOAc (0.196 g, 2 mmol) at 120 C during 20 h in DMAc (3 mL) in the presence of PdCl(C3H5)(dppb) (12.2 mg, 0.02 mmol) under argon affords 49 in 48% (0.181 g) yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With potassium phosphate; [5-(3-butylbenzimidazol-2-yliden-1-yl)-25,26,27,28-tetrapropyloxy calix[4]arene] (pyridine) palladium(II) dibromide; In 1,4-dioxane; at 100℃; for 24h;Inert atmosphere; | General procedure: In air, potassium phosphate (3mmol, 0.636g), catalyst 1 (0.08mol%, 0.0009g) and arylboronic acid (2mmol) were weighed into a 50mL glass vial that was sealed with a septum and purged with N2 (3×). Dioxane (1mL) was then injected via syringe followed by the aryl bromide (1mmol) (if liquid). If the aryl bromide was a solid, it was introduced into the vial prior to purging with N2. At this time, the reaction stirred for 24h at 100C. The reaction mixture was concentrated in vacuo and directly purified via silica gel flash chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
n-Butyllithium (2.063ml, 5.16 mmol) was added to -40 C solution of 1 -bromo-4-(trifluoromethyl)benzene (0.722 ml, 5.16 mmol) in THF (30 ml) and this solution was stirred at -40 C for 1 h. A solution of <strong>[113118-82-4]5-chloronicotinaldehyde</strong> (730 mg, 5.16 mmol) in THF (5 mL) was added and the solution was stirred at -40 C for 1 h and then at 0 C for 1 h. The reaction was then quenched with saturated aqueous NH4C1 solution. The product was extracted with ethyl acetate. The organic extract was dried over Na2504, filtered, and concentrated. No further purification is necessary. ?H NMR (500 MHz, CDC13) oe: 8.54 (s, 1H), 8.48 (s, 1H), 7.78 (s, 1H), 7.66 (d, J= 8 Hz, 2H), 7.53 (d, J= 8 Hz, 2H), 5.97(s, 1H), 3.55 (broad s, 1H). |
Tags: 4-Bromobenzotrifluoride | Trifluoromethyls | Fluorinated Building Blocks | Bromides | Aryls | Organic Building Blocks | 402-43-7
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H305 | May be harmful if swallowed and enters airways |
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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