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Chemical Structure| 643-58-3

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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.

Keywords: nanoporous organic polymer ; heterogeneous catalyst ; Suzuki−Miyaura coupling reaction ; size-selective reaction ; catalyst processing

Alternative Products

Product Details of [ 643-58-3 ]

CAS No. :643-58-3
Formula : C13H12
M.W : 168.23
SMILES Code : CC1=CC=CC=C1C2=CC=CC=C2
MDL No. :MFCD00008517
InChI Key :ALLIZEAXNXSFGD-UHFFFAOYSA-N
Pubchem ID :12563

Safety of [ 643-58-3 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of [ 643-58-3 ]

* 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.

  • Downstream synthetic route of [ 643-58-3 ]

[ 643-58-3 ] Synthesis Path-Downstream   1~3

  • 1
  • [ 615-37-2 ]
  • [ 98-80-6 ]
  • [ 643-58-3 ]
YieldReaction ConditionsOperation in experiment
98% With potassium carbonate; at 80℃; for 0.416667h;Green chemistry; General procedure: In a typical reaction, an overpressure screw-capped vialwas charged with arylhalides (1mmol), phenylboronicacid (1.2mmol), base, and catalyst and PEG (4mL). Thereaction mixture was stirred at appropriate temperature.After completion of the reaction as monitored by thin layerchromatography (TLC), the reaction mixture was cooledto room temperature; the catalyst was separated by a permanentmagnet, washed with water and EtOH, and storedfor the next run. The residual mixture was diluted withH2Oand the organic phase was extracted with dietyl ether(4 × 15mL). The extracted organic layers were dried overNa2SO4,filtered and concentrated under reduced pressureto get the desired product. These crude products were purifiedby recrystallization.
98% With sodium hydroxide; for 0.25h;Sealed tube; General procedure: A mixture of arylhalides (1 mmol), phenylboronic acid (1.2 mmol), base and PEG (4 mL)was placed in an overpressure screw-capped vial. An appropriate amount of the catalystwas added to the mixture and the mixture was stirred at the appropriate temperature.The progress of the reaction was monitored by thin-layer chromatography (TLC)until complete consumption of the aryl halide. The catalyst was separated by magneticdecantation, washed with water and EtOH, and stored for the next run. The residualmixture was diluted with H2O and the organic phase was extracted with diethyl ether(4x15 mL). The extracted organic layers were dried over Na2SO4, filtered, and concentratedunder reduced pressure to get the desired product. These crude products werepurified by recrystallization.
97% With potassium carbonate; In ethanol; water monomer; at 60℃; for 1.5h;Green chemistry; General procedure: A mixture of aryl halide (0.125mmol), phenylboronic acid(0.126mmol), K2CO3(0.187mmol), in 0.5ml H2O:EtOH(1:1) and Pd(II)NA2SMNP (0.0006g, 0.02mol%) wasstirred at 60C for the appropriate of time. The progressof the reaction was monitored by TLC. After completionthe reaction, the catalyst was removed with an externalmagnet and washed with EtOH, dried and used directly fora subsequent round of reaction without further purification.Then, desired product (liquid phase) was extracted byplate chromatography eluted with n-hexane/EtOAc (10:1).
96% With tripotassium phosphate tribasic; In water monomer; N,N-dimethyl-formamide; at 100℃; for 0.5h; General procedure: A sealed tube was charged with aryl halide (1.0 mmol), arylboronic acid (1.5 mmol), K3PO4 (2.0 mmol), DMF/H2O (v/v = 1:1, 2 mL) and catalyst (0.1 mol% Pd), the mixture was stirred at 100 C for a certain time under air atmosphere. After being cooled to room temperature, the mixture was diluted with CH2Cl2 and filtered. The organic phase was separated and dried over Na2SO4. The solvent was removed under vacuum and the residual was purified by column chromatography on silica gel with EtOAc/petroleum ether as eluent.
95% With potassium carbonate; at 80℃; for 1h;Green chemistry; General procedure: A mixture of aryl halides (1 mmol), phenylboronic acid (1.2 mmol),K2CO3 (1.5 mmol), PEG (polyethylene glycol) (4 mL) and Pd catalyst(10 mg) was stirred at 80 C temperature for a given time until the completion of the reaction was achieved as monitored by TLC. After completion of the reaction, the catalyst was separated with a magnetand washed with EtOH, dried and reused for a next run under the same reaction conditions. To the resulting mixture H2O (10mL) was added followed by extraction with dietyl ether (3× 50mL). The extracted organic phases were dried over Na2SO4, filtered and concentrated invacuo to get the desired product. These crude products were puried by a short plug of silica using hexane/ethyl acetate as eluent.
95% With potassium carbonate; In ethanol; at 80℃; for 3h;Inert atmosphere; General procedure: A mixture of 1a (102 mg, 0.5 mmol), phenylboronic acid 2a(91.4 mg, 0.75 mmol), and K2CO3(138 mg, 1.0 mmol) in EtOH (3 mL) was heated in the presence of SGlPd at 80C for 3 h under argon an atmosphere without stirring. After the reaction mixture was cooled to room temperature, the SGlPd was removed from the reaction mixture and rinsed several time with EtOH. The raction mixture was poured into 2 MNaOH aq., extracted with AcOEt. The organic layer was washed with sat. aq. NH4Cl, and sat. aq. NaCl, dried over anhydrous NaSO4. Concentration at reduced pressure gave yellowish oil, which was chromatographed on silica gel with hexane as the eluent to give the biphenyl (3a, 77.1 mg, 99%) as a colorless solid. The recovered SGlPd catalyst was again subjected to next reaction for second run. The procedure was repeated a total 10 runs.
95% With potassium carbonate; In water monomer; at 80℃; for 6h;Green chemistry;Catalytic behavior; General procedure: Forthe Suzuki-Miyaura reaction, a 50 mL round-bottomed flask was charged with aryl halide(0.5 mmol), arylboronic acid (0.65 mmol), K2CO3 (1 mmol), catalyst (0.002 g; 0.0005 mmol ofPd) and water (4 mL) and stirred at appropriate temperature. The progress of the reaction wasmonitored by thin layer chromatography using aluminum coated TLC plates (Merck) underUV light. At the end of reaction, the mixture was cooled down to room temperature and theproduct diluted with water (10 mL) and extracted with ether (3 x 15 mL). The combinedextract was washed with brine (3 x 15 mL) and dried over Na2SO4. After evaporation of the solventunder reduced pressure, the residue was subjected to column chromatography with ethylacetate/hexane (1:9) as eluent to get the desired product.
95% With potassium carbonate; In water monomer; at 60℃; for 1.5h;Green chemistry; General procedure: A mixture of Fe3O4(at)SiO2-NHC-Pd(II) (0.006 g, 0.37 mol%), arylboronic acid (1.1 mmol), aryl halide (1.0 mmol), and K2CO3(2 mmol) in H2O (3 mL)was stirred at 60 C for the appropriate timeas indicated in Table 3. The completion of the reaction was monitoredby TLC. After completion of the reaction, the catalyst wasremoved by an external magnetic field and was then washed withH2O (5 mL) and ethyl acetate (10 mL). The organic layer was separated,dried over anhydrous Na2SO4, and filtered. Then, the solventwas evaporated under reduced pressure. The pure product wasobtained via silica gel column chromatography with an eluent of nhexaneand ethylacetate.
94% With anhydrous potassium acetate; In ethanol; dimethyl sulfoxide; at 100℃; for 14h;Schlenk technique; Inert atmosphere; General procedure: A definite amount of palladium catalyst and base were placed in an oven dried 25 mL Schlenk tube, and the reaction vessel was evacuated and filled with nitrogen for three times. Aromatic halide(0.5 mmol), phenylboronic acid (0.75 mmol), and solvent (5.0 mL) were added with a syringe, and the resulting mixture was stirred at 100 C for a desired time. After cooled down to room temperature, the reaction mixture was filtered and washed with brine and diethyl ether. The combined organic layers were washed with a saturated solution of sodium hydrogen carbonate and then with brine,dried over Na2SO4. Solvent was removed under a reduced pressure,and the reaction products were purified by silica gel chromatography with a mixture of n-hexane and ethyl acetate
94% With trimethyl-(2-hydroxyethyl)ammonium chloride; potassium carbonate; In glycerol; at 80℃; for 1.5h;Sealed tube; General procedure: Typically, a 10 mL screw-capped vial was charged with arylboronicacid (1.1 mmol), aryl halide (1 mmol), K2CO3 (2 mmol),GO/Fe3O4G2/Co (1 mg, 0.4 mol %), and DES (ChCl:glycerol,3 mL). Afterward, the vial was put at 80 C to form the correspondingcoupling products (monitored by TLC). After completing thereaction, the catalyst was collected with a magnet and the reactionmixture was quenched with water and extracted with ethyl acetate(3 5 mL). The organic layer was dried with MgSO4 and evaporatedunder vacuum to yield the crude product, which was thenpurified by column chromatography using silica gel. Finally, theproducts were subjected to structural identification by 1H and13C NMR spectroscopies.
93% With C28H40Br4N4Pd2; potassium carbonate; In water monomer; acetone; at 20℃; for 0.75h; General procedure: A mixture of aryl halide (1 mmol), arylboronic acid (1.2 mmol), catalyst A (1 mol %, 0.0096 g), K2CO3 (2 mmol), and (1:1) acetone/water mixed solvent (3 mL) were taken in 25 mL round bottom flask and the mixture was stirred at room temperature (40 C for heteroaryl halides) until the completion of reaction (required time given in Tables 3-5). The reaction mixture was then diluted with water (20 mL) and extracted three times with dichloromethane (3×10 mL). The combined organic layer was washed with brine (20 mL) and dried over anhydrous Na2SO4. After that it was concentrated under reduced pressure and the crude product was purified by column chromatography on silica gel (60-120 mesh) using petroleum ether (60-80 C) and ethyl acetate were as the eluent.
93% With potassium carbonate; In water monomer; N,N-dimethyl-formamide; at 60℃; for 3h; General procedure: An RB flask was charged with aryl halide (1.0mmol), arylboronic acid (1.5mmol), K2CO3 (2mmol), DMF/H2O (v/v=1:1, 4mL) and catalyst (0.1mol% Pd); the mixture was magnetically stirred at 60C under air atmosphere. After 2-7h, the reactions were completed (TLC). The mixture was cooled to room temperature, Et2O (10mL) and H2O (5mL) were added, and filtered. The organic phase was separated and dried over MgSO4. The solvent was evaporated and the residual was purified by preparative TLC on silica gel plates eluting with n-hexane/EtOAc=9:1. All the products were known compounds and were identified by comparison of their physical and spectroscopic data with those of authentic samples.
92% With ϖ-allylpalladium (II) chloride dimer; potassium carbonate; In water monomer; at 50℃; for 24h; General procedure: 1Gn[CO2K] was prepared by mixing 1Gn[CO2H] (0.0184 mmol) and potassium hydroxide (1.1 equiv/CO2H) at room temperature in water (1.5 mL) under an argon atmosphere. By the addition of [PdCl(η3-C3H5)]2 (0.0084 mmol) to 1Gn[CO2K] aqueous solution, the 1Gn[CO2K]-palladium catalyst was prepared with stirring for 15 min. To a mixture of 5 (3.34 mmol), 6 (5.01 mmol), and potassium carbonate (15.0 mmol) in water (5.2 mL) was added the above-prepared 1Gn[CO2K]-palladium aqueous solution at 0 C. The resulting mixture was stirred for 4 h at 50 C. The reaction mixture was extracted with diethyl ether four times, and the combined organic layers were washed with brine then dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified with silica gel column chromatography to obtain the coupling product 7.
92% With potassium hydroxide; at 100℃; for 4.5h; General procedure: Aryl haide (1mmol), phenylboronic acid (1mmol), KOH(3mmol) and 0.004g of catalyst were added to 1mL ofPEG-400 and the reaction mixture was stirred at 100Cfor a certain period of time. After completion the reaction,the mixture was filtered to collect the catalyst andthe organic phase of the filtrate was extracted twice withEtOAc and dried over Na2SO4to afford the correspondingpure products.
92% With potassium carbonate; In ethanol; water monomer; at 80℃; for 1h;Green chemistry; General procedure: A mixture of phenylboronic acid (1.0 mmol), aryl halide (1.0 mmol), MCM-41PCA/Pd (0.008 mol%) catalyst and K 2 CO 3 (3.0 mmol) was stirred in 3 mL of aqueous-ethanol (1:1 (v/v)) at 80 C. After completion of the reaction, checked by TLC, The MCM-41PCA/Pd catalyst was collected using a centrifuge and rinsed with ethanol and distilled water to eliminate the unreacted reagents. Then, the product was extracted with diethyl ether and rinsed using distilled water and dried over anhydrous Na 2 SO 4. The product was purified by a plate to give the desired product.
91% With palladium; potassium hydroxide; In water monomer; at 100℃; for 12h;Green chemistry; reactionTo a mixture of aryl iodide (1.0 mmol), phenylboronic acid(1.2 mmol), and potassium hydroxide (2.0 mmol), 10 mL of the PdNPs solution (1.0 mol%) in water was added. The reaction mixturewas then stirred at 100C for 12 h. The progress of the reaction wasmonitored using TLC. After completion of the reaction, the reac-tion mixture was cooled to room temperature and extracted withEtOAc three times. The combined extracts were dried over anhy-drous MgSO4and the solvents were removed under vacuum. Thecrude products were then purified by flash chromatography on sil-ica gel to give the desired coupling products and characterized by1H NMR. All the products are known compounds and the spectral data and melting points were identical to those reported in the literature
91% With potassium hydroxide; In water monomer; at 100℃; for 2h;Green chemistry; General procedure: To a mixture of aryl iodide (1.0 mmol), phenylboronic acid(1.2 mmol), and potassium hydroxide (2.0 mmol), 10 mL of the PdNPs solution (1.0 mol%) in water was added. The reaction mixturewas then stirred at 100C for 12 h. The progress of the reaction wasmonitored using TLC. After completion of the reaction, the reac-tion mixture was cooled to room temperature and extracted withEtOAc three times. The combined extracts were dried over anhy-drous MgSO4and the solvents were removed under vacuum. Thecrude products were then purified by flash chromatography on sil-ica gel to give the desired coupling products and characterized by1H NMR. All the products are known compounds and the spectraldata and melting points were identical to those reported in theliterature [1-3].
91% With potassium carbonate; In water monomer; at 90℃; for 0.5h; General procedure: Mixture of iodobenzene (0.5 mmol), boronic acid(0.75 mmol), K2CO3 (1.25 mmol), PdNP-PG catalyst(0.1 mol %), and water as a solvent (2 mL) was stirred at 90 C for appropriate time as indicated in Table 1 entry 5.The progress of the reaction was monitored by TLC. The reaction mass was cooled after completion of the reaction and the catalyst was separated by filtration. The product was extracted from aqueous layer by using 10 mL ethylacetate. The combined organic layer was dried on anhydrous sodium sulphate, concentrated under reduced pressure and was purified by column chromatography on silicagel (Hexane/EtOAc: 98:2) to get the product.
91% With potassium carbonate; for 1.5h;Heating; Green chemistry;Catalytic behavior; General procedure: The Fe3O4-Schiff base-Pd (0.91 mol%) was added to mixtureof aryl halides (1 mmol), phenylboronic acid (1 mmol)and K2CO3(3 mmol) in 2 mL of PEG-400 (polyethylene glycol)at 80 C, and the mixture was stirred for the appropriatetime. Completion of the reaction was indicated using TLC.After completion of the reaction, the catalyst was separatedwith an external magnet, then product was extracted with10 mL of H2Oand ethyl acetate (3 × 10 mL). The organiclayer was dried over Na2SO4.Then, the solvent was evaporated,and corresponding biphenyl was obtained in good tohigh yield.
90% With potassium carbonate; In water monomer; at 50℃; for 5h; General procedure: A mixture of aryl halide (1 mmol), phenylboronic acid (1 mmol) or sodium tetraphenyl borate (0.5 mmol), K2CO3 (3 mmol), and Pd-SMU-MNPs (0.006 g, 0.92 mol %) was added to a reaction vessel. The resulting mixture was stirred in H2O or PEG-400 at 50 C and the progress of the reaction was monitored by TLC. After completion of the reaction, the catalyst was separated by an external magnet and washed with ethylacetate. The reaction mixture was extracted with H2O and ethylacetate and the organic layer was dried over anhydrous Na2SO4 (1.5 g). Then the solvent was evaporated and pure biphenyl derivatives were obtained in good to excellent yields.
90% With potassium carbonate; at 100℃; for 1.23333h; General procedure: A mixture of aryl halide (1 mmol), phenylboronic acid (1.2 mmol), K2CO3 (1.5 mmol), nanocatalyst (25 mg) and PEG (4 mL) was placed in an overpressure screw-capped vial and stirred at 100 C for the required reaction time. After completion of the reaction, as judged by TLC, the reaction mixture was cooled to room temperature. The catalyst was separated by magnetic decantation, washed with water and EtOH and dried for the next run. The decantate was diluted with H2O (10 mL), and the organic phase was extracted with diethyl ether (3 x 20 mL). The organic extract was dried over Na2SO4, filtered and concentrated under reduced pressure to get the desired product. These crude products were purified by recrystallization.
90% With triethylamine; In neat (no solvent); at 70℃; for 1.5h;Sealed tube; Irradiation; General procedure: In a typical reaction, a mixture of aryl halid (0.2mmol),arylboronic acid (0.22 mmol), Et3N(0.4 mmol) and TiO2-AA-Pd nano hybrid (0.15mol%) was added in a10 mL Pyrex test tube and sealed with septum cap. Then thereaction mixture transferred into a reactor chamber and irradiate dunder magnetic stirring using a CFL lamp (philips,wavelength in the range 390-750nm, 40W, 1.1Wm-2) asthe visible light source at 70C for appropriate time. Aftercompletion of the reaction, TiO2-AA-Pd nanohybrid wasextracted by adding of ethanol (5mL) followed by centrifugingand decantation (3 × 5mL ethanol). Then, desired product(liquid phase) was extracted by plate chromatographyeluted with n-hexane/EtOAc (10/2).
90% With dimethylammonium chloride; potassium carbonate; In glycerol; for 0.833333h;Heating; General procedure: A mixture of aryl boronic acid (1.1mmol), aryl halide (1.0mmol), K2CO3 (2.0mmol), and Fe3O4/GOCL-Pd (0.005g, 0.2mol%) in 3mL of DES (DMAC:Gly) was stirred at 80C for given time. The extent of reaction was checked using thin layer chromatography. At the end of reaction, the mixture diluted with 15mL of water and extracted with ethyl acetate (3×10mL). After removing the volatiles from the organic fraction, the residue was purified by column chromatography on silica gel with an eluent consisting of ethyl acetate and n-hexane to achieve the desired product. The products were characterized by 1H NMR and melting point followed by comparison with authentic standard samples. The aqueous phase, which contained both of the catalyst and DES, was used for another run after evaporation of water.
90% With nanocellulose; palladium diacetate; potassium carbonate; In water monomer; at 60℃; for 0.4h;Green chemistry; General procedure: To a mixture of Pd(OAc)2 (0.1 mol%) and NC (1 wt%) was added 3 mL of water, aryl halide (0.4 mmol) and phenylboronic acid (0.48 mmol, 1.2 eq.). The resultant reaction mixture was stirred at appropriate temperature (Table 3 of the manuscript). After completion of the reaction as indicated by the thin layer chromatography, the reaction mixture was subjected for filtration and the filtrate was extracted with etyl acetate (EtOAc) for the separation of products. The EtOAc portion was then evaporated and used for the purification of the biaryls using column chromatography employing a mixture of EtOAc and hexanes as eluent
89% With C22H20N4O6Pd; potassium carbonate; In water monomer; at 100℃; for 6h;Green chemistry; General procedure: Aryl halide (1 mmol), phenylboronic acid (1.5 mmol), palladium complex (1 mol%), K2CO3 (1.5 mmol), and water (1.5 mL) were added to 5 mL flask and mixture was stirred at 100 C for appropriate reaction time. The progress of the reaction to completion was monitored by TLC or GC analysis. After the completion of reaction, the aqueous layer was extracted with ethyl acetate or diethyl ether (51 mL). Organic extracts were combined to gether and dried over anhydrous Na2SO4 and purified by flash chromatographyusing hexane/EtOAc to give the desired coupling product.
89% With C37H28N8O*2Cl(1-)*Pd(2+); potassium carbonate; In ethanol; at 70℃; for 2h; General procedure: Arylhalide (5.0 mmol) and phenylboronic acid (5.0 mmol), K2CO3 (5.0 mmol) and X-Pd3L (0.005 mol% Pd loading) were added to a solutionof 12 mL EtOH under ambient atmosphere. The mixture was stirred at 70 C for 2 h. After cooling, H2O (10 mL) was added into the resultant mixture and the product was extracted by ethyl acetate (3 × 10 mL). The organic phase was combined and dried over Na2SO4. After removal of solvent, the product was dried at 60 C. In most cases, the products are pure (analyzed by 1H NMR spectroscopy) because it is an equal stoichiometric reaction and the substrates are completely converted into product. If the product is impure, the purification can be performed ona silica gel chromatography (hexane:ether = 60:1 as an eluent). All products were confirmed by 1H and 13C NMR and compared with literatures (see SI). For the recycled experiment, the xerogel catalyst was recovered by centrifugation and washed with EtOH (3 × 4 mL) after reaction, then dried in air.
88% With Cs2CO3; In ethanol; at 80℃; for 15h; General procedure: To a round-bottom flask, aryl electrophile (1.0mmol), Pdnanocatalyst (1.5 mol%), Cs2CO3(1.5 mmol), PhB(OH)2(1.3 mmol), and EtOH (3.0 mL) were added, stirred andheated at 80C. The progress of the reaction was checked using TLC. After the completion of the reaction, the mixturewas cooled down and the catalyst was isolated usingan external magnet. The solvent was evaporated and furtherpurification was achieved using column chromatography onsilica gel to deliver the desired biphenyl derivatives in highyields.
88% With potassium carbonate; at 100℃; for 0.916667h;Catalytic behavior; General procedure: 0.008 g of catalyst was added to a mixture of aryl halide(1.0 mmol), phenylboronic acid (1.0 mmol) and K2CO3 (3.0 mmol)in 1 mL of PEG-400. The mixture was stirred at 100 C in an oil bathfor a certain period of time. Completion of the reaction waschecked by TLC, then the catalyst was separated with filtrationand the organic phase of the filtrate was extracted with Et2O anddried over Na2SO4 to afford the corresponding product.
85% With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 5h; General procedure: To a suspension of aryl halide (1.0mmol), K2CO3 (2.0mmol) and Pd complex (0.3mol %) in DMF (5mL) phenylboronic acid (1.2mmol) was added. The reaction mixture was stirred at 80C for an appropriate time. After completion of the reaction, the procedure was followed as outlined in Section 2.6.
85% With potassium carbonate; In ethanol; water monomer; at 60℃; for 2.5h;Catalytic behavior; General procedure: A mixture of Pd NPs-HNG nanocomposite (0.025-0.1 mol% ofPd), K2CO3(3 mmol), aryl halide (1.0 mmol), aryl boronic acid(1.3 mmol), and EtOH/H2O (2 mL, 1:1) was stirred in air at 60C.After completion of the reaction as indicated by TLC, the hetero-geneous mixture was cooled to room temperature and filteredthrough a pad of celite. The filtrate was concentrated and then theresidue was purified by thin-layer chromatography (ethyl acetateand n-hexane) to yield a pure product. The catalyst was recoveredby filtration and washed extensively with acetone and drying in theair.
83% With potassium carbonate; In water monomer; at 100℃; for 3.5h;Green chemistry; General procedure: A mixture of phenylboronic acid (1.0 mmol), aryl halide (1.0 mmol), K2CO3 (6.0 mmol) and Pd(at)CC-SO3H-NH2 catalyst (10 wt%) were heated in water (3 mL) at 100 C. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was cooled, the catalyst was filtered off and the filtrate was extracted with ethyl acetate. The ethyl acetate layer was dried over sodium sulphate and then concentrated under reduced pressure. The concentrated mass was then purified by column chromatography using petroleum ether/ethyl acetate to obtain the biaryl product.
82% With potassium dihydrogen orthophosphate; In ethanol; water monomer; at 70℃; for 0.5h; General procedure: A mixture of aryl halide (0.5 mmol), phenylboronic acid (0.7 mmol),potassium phosphate (1.0 mmol) and catalyst (0.1 mol% of Pd) inEtOH/H2O (1:1, 4 mL) as a solvent was mixed in a round bottom flask(10 mL). Then, the resulting mixture stirred at 70 C. The progress of thereaction was monitored by Thin Layer Chromatography (TLC). Afterreaction completion, the catalyst was separated by centrifugation andCH2Cl2 was added. The CH2Cl2 layer was separated from the waterlayer using a separatory funnel and followed by drying of the organiclayer over Na2SO4. The dried CH2Cl2 layer was concentrated undervacuum, and the product was purified by thin-layer chromatography(SiO2, n-hexane and ethyl acetate) to isolate the corresponding products.The catalyst was washed with EtOH (2×10 mL) and H2O(2×10 mL), and was reused for the next run.
80% With potassium hydroxide; In ethanol; for 0.1h;Microwave irradiation; General procedure: In a microwave tube, Fe3O4SiO2-AEAPTMS-Pd(II) catalyst 1 (0.006 mmol, 0.06 mol%) followed by boronic acid (0.75 mmol), aryl halide (0.5 mmol), KOH (0.75 mmol) and 1,5 mL of ethanol. The reaction tube was transferred to a microwave oven and irradiated at 40 W for 6 min. After the completion of the reaction and separation of catalyst with a permanent magnet, the product was extracted from the catalyst by washing with ethanol and ethyl acetate. The solvents and volatiles were completely removed under vacuum to give the crude product. The resulting crude compound was purified by flash column chromatography on silica gel (hexane:ethyl acetate, 95:0.5).
80% With potassium carbonate; In ethanol; water monomer; at 20℃; for 0.5h;Green chemistry; General procedure: The novel nanocatalyst (0.2 mol%), the aryl halides (1.0 mmol), phenylboronic acid (1.1 mmol), K2CO3 (2.0 mmol) and EtOH/H2O (1:1) (3 mL) were added to a round bottomed flask and stirred for the desired time at room temperature (Scheme 1). The reaction was monitored by thin layer chromatography (TLC, n-hexane/acetone; 4:1). When the reaction was completed, 5 mL of ethanol was added and an external magnet removed the catalyst. Further purification was achieved by column chromatography
80% With potassium-t-butoxide; In water monomer; at 100℃; for 3h; General procedure: A round-bottom flask was charged with an aryl halide (1 mmol),phenylboronic acid (1.2 mmol), Bi2S3 microspheres (60 mg), and potassiumt-butoxide (3 mmol). The resulting mixture was stirred in H2O at100 C. The reaction was monitored by TLC. At the end of reaction, ethylacetate (20 mL) was added and filtrated. After concentration, the residuewas subjected to column chromatography on silica gel to yield thedesired product.
80% With anhydrous sodium carbonate; In dimethyl sulfoxide; at 100℃; for 0.583333h;Catalytic behavior; General procedure: A mixture of aryl halide (1 mmol), 1 mmol of phenylboronicacid (PhB(OH)2), Na2CO3 (3 mmol, 0.318 g), andCu-MPAMPFe3O4 (15 mg in 2 mL PEG at 80C) or ZrOMPAMPFe3O4 (15 mg in 2 mL DMSO at 100C) wasstirred and the progress of the reaction was monitored by TLC. After completion of the reaction, the mixture wascooled down, the catalysts were separated using an externalmagnet and washed with ethyl acetate. The remaining reactionmixture was extracted with water and ethyl acetate. Theorganic layer was dried over anhydrous Na2SO4 (1.5 g).Then ethyl acetate was evaporated to obtain pure biphenylderivatives.
79% With potassium carbonate; at 60℃; for 6.25h; General procedure: In a 25-mL glass balloon, Pd-BS-MCM-41 catalyst (12 mg)was added to a mixture of aryl halide (1.0 mmol), PhB(OH)2and base (3 mmol) in PEG at 60 C. The reaction followedfor the times exhibited in Table 2. (The progress of reactionswas monitored by TLC, eluent; n-hexane: acetone, 8:2.)Then, the catalyst was separated from the reaction crude bysimple filtration, and the organic residue was extracted bydecantation with diethyl ether and water. After evaporationof the organic phase, the pure final product was obtained.
77% With potassium carbonate; In methanol; at 40℃; for 4.5h; a definite amount ofpalladium catalyst (1) and base were placed in a dried 25mLround bottom flask, aromatic halide (1.0mmol), phenylboronicacid (1.5mmol) and solvent (6.0mL) were added, andthe mixture was stirred at 40C for a desired time. Afterthat, the reaction mixture was quenched with water andextracted with ethyl acetate. The combined organic layerswere dried over anhydrous Na2SO4.Solvent was removedunder a reduced pressure and the crude product was purified by silica gel chromatography with a mixture of petroleumether and ethyl acetate.
73% With potassium carbonate; In water monomer; for 7h;Reflux; General procedure: A mixture of phenylboronicacid (5, 1.5 mmol), aryl halide 6a-6j(1.0 mmol), K2CO3 (5.0 mmol), H2O (5 mL), andPdCl2/SMI (0.02 g) was stirred under reflux(Scheme 2). The reaction progress was monitoredusing thin-layer chromatography (TLC) (n-hexane-EtOAc, 2:5). After completion of the reaction, themixture was filtered through a Büchner funnel. Theprecipitate was washed with acetone several times,dried under reduced pressure at 70C for 3 h, andextracted with methylene chloride (3×5 mL). Thesolvent was removed on a rotary evaporator, and thecrude product was purified by flash column chromatographyusing hexane or hexane-ethyl acetate as eluent.The products, symmetrical and unsymmetrical biaryls7a-7h were characterized by their melting points, IRand 1H and 13C NMR spectra, and by comparison oftheir physical data with those reported in the literature[24, 25].
72% With tripotassium phosphate tribasic; PdPt(2-diphenylphosphinopyridine)2Cl2; In water monomer; at 25℃; for 24h; General procedure: Aryl halide (1mmol), arylboronic acid (1.5mmol), catalyst (0.8mol%), K3PO4 (1.5mmol) and distilled water (2mL) were added to a 5mL flask. The mixture was stirred for appropriate reaction time at 25C for aryl iodides, 60C for aryl bromides and 80C for aryl chlorides. The progress of the reaction was monitored by GC. After completion of the reaction, the aqueous layer was extracted with ethyl acetate or hexane (5×1mL) and further purified by column chromatography using hexane and ethyl acetate as an eluant. 1a.
72% With potassium carbonate; In neat (no solvent); for 0.1h;Schlenk technique; Microwave irradiation; General procedure: In a Schlenk tube, PhB(OH)2 (1.8 mmol), aryl halide (1.0 mmol),Pd NPsSch-boehmite (0.005 mol%) and K2CO3 (3.5 mmol) wereirradiated in a microwave oven for 6 min. The used catalyst wasseparated from the reaction mixture by filtration for the next cycleof catalytic reaction after completion of the reaction. The ensuingreaction mixture was extracted with H2O/toluene (1:2 v/v) and theorganic phase was concentrated via evaporation under reducedpressure to obtain the desired biaryls which were then identified byGC/MS analyses.
72% With potassium carbonate; In water monomer; for 7h;Reflux; General procedure: A mixture of aryl halide 6 (1.0 mmol), phenylboronic acid 5 (1.5 mmol, 0.18 g), K2CO3 (5.0 mmol, 0.69 g), H2O (5 mL), and 0.02 g of SMI-PdCl2 was stirred under reflux. Reaction progress was monitored by TLC in hexane-ethyl acetate (2 : 5). After completion of the reaction, the precipitate that formed was filtered off, washed with several portions of acetone, and dried under reduced pressure at 70C for 3 h. The product was extracted with CH2Cl2 (3 × 5 mL), and the solvent was removed on a rotary evaporator. The crude product was purifi ed by fl ash column chromatography (hexane or hexane-ethyl acetate).
69% With potassium carbonate; In neat (no solvent); for 0.1h;Schlenk technique; Microwave irradiation; Green chemistry; General procedure: A mixture of Pd NPsCS-AC/Fe3O4 (1.5 × 10-3 mmol),phenyl boronic acid (1.8 mmol), aryl halides (1.0 mmol),K2CO3(3.5 mmol) were added to a Schlenk tube, and it was heated under microwave irradiation at 400 W for 6 min.After the completion of coupling reaction, the mixture was cooled at room temperature, and it was extracted with water:toluene (1:2 v/v). Finally, desire biaryls were collected by evaporation of organic phase under reduced pressure and characterized by GC/MS analyses.
67% With potassium carbonate; In neat (no solvent); for 0.0833333h;Microwave irradiation; Schlenk technique; Green chemistry; General procedure: In the process of determination of the fabricated catalyst efficiencyin Suzuki coupling reactions, microwave irradiation technique,which is very fast, easy to use, highly productive andnontoxic, was used. Firstly, the reaction of phenylboronic acid and4-iodoanisol was selected as the model coupling reaction for thesynthesis of biaryl compounds by Suzuki coupling reactions. Then,the effects of catalyst loading, reaction time, base type, and microwaveirradiation power on the biaryl product yield wereinvestigated on the chosen model coupling reaction. After the optimumreaction conditions were found, the general method whichwas performed for the fabrication of different biaryls by Suzukicoupling reactions was as follows: 1.87 mmol of phenyl boronicacid, 1.12 mmol of the selected aryl halide, 3.75 mmol of potassiumcarbonate, and 0.007 mol% of Pd NPsP(3-MPAP) were added in aSchlenk tube. The coupling reactions were performed in solventfreemedium using 400W microwave irradiation for 5min. Theobtained mixture was cooled to room temperature (RT) at the endof the reaction. 5mL toluene was added on the cooled mixture andit was filtered. Then, the filtrate was extracted with 5mL watertwice. MgSO4 was added on the separated organic phase whichcontains biaryl product to completely eliminate water. Then,toluene in the obtained product was evaporated at room temperature.Finally, the product yield was calculated and its chemicalstructure was identified by GC/MS analysis.
57% With potassium carbonate; In neat (no solvent); at 50℃; for 0.0666667h;Microwave irradiation; Green chemistry;Catalytic behavior; General procedure: Base system, reaction time, and catalysts amount parameters must be optimized to obtain C-C coupling reactions with high selectivity. Therefore, coupling reaction of 4-bromoanisol with phenylboronic acid was selected as the model reaction, and optimum conditions were determined for coupling reaction in the presence of biomaterial supported Pd catalyst. To determine the optimum catalyst amount, biomaterial supported Pd catalyst was used at different loading catalyst (2.5, 5.0,10.0, 20.0) × 10-3 mol% under microwave irradiation at 400 W insolvent insolvent-free reaction mixture (50C). Reaction time was investigated from 1 min to 5 min, and NaOH, K2CO3, KOH, and Cs2CO3 base systems were examined for optimum coupling reaction condition. Different aryl halides (1.12 mmol), K2CO3 (3.75 mmol), phenylboronic acid (1.87 mmol), and biomaterial supported Pd catalyst (0.01% mol) were mixed, and the reaction was allowed under microwave irradiation at 400 W in solvent-free media for 4 min (Scheme 2). At the end of the reaction period, the product was extracted with toluene:water (4:2, v:v). Organic phase was separated, and MgSO4 was added to remove water. The chemical identifications of synthesized biaryls were illuminated with 1H NMR and gas chromatography-mass spectroscopy (GC-MS) analyses. At the end of the coupling reaction, biomaterial supported Pd catalyst was filtered and washed with hot water and methanol to reactivate the biocatalyst. Then, the same biomaterial supported Pd catalyst was used for recycling experiments for model reaction under optimum reaction conditions for 10 times. Leaching test was applied to supernatant of all recycle experiments to determine Pd ion in the solution.
57% With potassium carbonate; In water monomer; at 80℃; for 2h; General procedure: Pd/IG biocatalyst (0.02 g, 1 mol%) was added to a glasstube containing arylboronic acid (1.15 mmol), aryl halide(1.0 mmol) and K2CO3(1.5 mmol) in water (2 mL) andwas heated at 80 C for the period of time listed in Table 2. After completion of the reaction (monitored by TLC), thecatalyst was separated via centrifuging and washed withwater and EtOAc to reuse for the next run. The filtrate wasevaporated under vacuum and extracted with chloroformand water. The organic layer was evaporated and the pureproduct was obtained by preparative TLC, eluting with ethylacetate/n-hexane and the yield was calculated based on thearyl halides.
56% With potassium carbonate; In water monomer; at 60℃; for 0.5h;Sonication; Green chemistry; General procedure: The mixture of 1.0 mmol aryl halides, 1.8 mmol phenyl boronic acid, 3.5 mmol base, 1x10-2 mmol Pd NPsCMC/AG and 6 mL of water were sonicated at 60C for 30 min. Formation of biphenyl compounds was followed by thin layer chromatography. After the coupling reactions, the reaction mixture was extracted with toluene. Organic phase, which containing biphenyl compounds, was separated with separation funnel and desired coupling products were obtained by evaporating of the solvent.
52% With potassium carbonate; In neat (no solvent); at 50℃; for 0.0666667h;Microwave irradiation;Catalytic behavior; General procedure: A mixture of the catalyst (0.02 mol%), aryl halide (1.12 mmol), phenyl boronic acid (1.87 mmol), and K2CO3(3.75 mmol) was irritated at 50C and 400 W for 4 min without solvent under microwave irradiation. After these reactions were completed, the mixture was extracted with toluene-water (4:2, v/v). Consequently, the organic phase was separated and dried with MgSO4. Finally, the obtained biaryl products were characterized by 1H NMR and GC-MS.
50% With 2-(4-chloro-2,6-dimethyl-3-(naphthalen-1-yl)-3λ,5,11λ-triaza-4-palladatricyclo[5.3.1.0,]undeca-1(10),2,5,7(11),8-pentaen-4-ylium )-5-((carboxymethoxy)methyl)chitosan chloride; potassium carbonate; In neat (no solvent); at 50℃; for 0.0666667h;Microwave irradiation; Green chemistry;Catalytic behavior; General procedure: A mixture of phenyl boronic acid (1.87 mmol), the newbiopolymer (chitosan)-based pincer-type Pd(II) catalyst (5 103%mol), K2CO3 (3.75 mmol) and aryl halide (1.12 mmol)was irradiatedin a microwave oven at 50 C, 400 W for 4 min in a solvent-freemedia. Following the reaction procedure, the reaction media wascooled and extracted with toluene:water (2:1). The organic phasewas separated and dried with MgSO4.
46% With potassium carbonate; In neat (no solvent); at 50℃; for 0.0666667h;Microwave irradiation; Green chemistry;Catalytic behavior; General procedure: Phenyl boronic acid (1.75 mmol), aryl halide (1.12 mmol), K2CO3(3.75 mmol) and the catalyst (0.02%) were mixed without usingany solvent and subsequently the mixture was exposed to themicrowave irradiation (at 400 W) at 50C for 4 min. After thereaction was terminated, the organic phase was extracted fromthe mixture into toluene-water (4:2 v:v). To ensure the completeremoval of water from the organic phase, MgSO4was added intothe organic phase. The chemical composition of the synthesizedbiaryls in the organic phase were analysed by using GC-MS AgilentGC-7890 A- MS 5975.
33% With potassium carbonate; at 50℃; for 0.0833333h;Microwave irradiation;Catalytic behavior; General procedure: The mixture of phenyl boronic acid (1.75 mmol), aryl halide(1.12 mmol), K2CO3(3.75 mmol) and the catalyst (5 × 10-3% mol)in a Schlenk tube was exposed to the microwave irradiation (at 400 W) at 50C for 5 min. The progress of the reactions was moni-tored by thin layer chromatography (TLC). Then, reaction mediumwas extracted with toluene-water mixture (2:1 v:v) and the organicphase was dried with addition of MgSO4. Finally, chemical identi-fication of the biaryls was done on a GC-MS.
32% With potassium carbonate; In neat (no solvent); at 50℃; for 0.1h;Microwave irradiation; Green chemistry;Catalytic behavior; General procedure: A mixture of 1.12 mmol aril halides, 1.18 mmol phenyl boronic acid, 3.75 mmol K2CO3 and CL-Sc-Pd catalyst (5 × 10-3mol%) was irradiated in a microwave oven at 50C and 400 W for 6 min in solvent-free medium. After the reaction, the mixture was cooled and extracted with toluene:water solution (2:1). The organic phase was separated with separatory funnel and MgSO4 was added to completely remove the water. Finally, the organic phase, which contained the biaryl compounds, was sent for GC/MS and 1H NMR analysis.
30% General procedure: Aryl iodide (1.0 mmol), arylboronic acid (2.0 mmol), Ni(NO3)26H2O (0.05 mmol), pre-ligand Pre-L1(0.05 mmol), base (3.0 mmol), and toluene (3 mL) were added to a glass tube, which was then sealed with aPTFE cap. After the reaction mixture was stirred vigorously at room temperature for 5 min, the sealed glasstube with the reaction mixture was placed in a Radleys Carousel 12 Plus Reaction Station, which waspreheated to the described temperature. After the reaction was stirred for the required time and then cooleddown to room temperature, water (10 mL) was added to the reaction mixture. The resulting mixture wasextracted with ethyl acetate (3 x 10 mL). The combined organic layers were dried over anhydrous Na2SO4,filtered and concentrated to dryness. The remaining residue was analyzed by GC (Table 1) or purified byflash chromatography on silica gel with ethyl acetate-hexanes (0-20% ethyl acetate in hexanes).
22% With oxygen; potassium carbonate; In neat (no solvent); at 50℃; for 0.0833333h;Microwave irradiation; Green chemistry;Catalytic behavior; General procedure: Upon determination of the optimum conditions, we employed the following procedure for the synthesis of biaryls. Phenyl boronic acid (1.75 mmol), aryl halide (1.12 mmol), K2CO3 (3.75 mmol) and the catalyst (1.5×10-3mol %) were put into a Schlenk tube and exposed to 400 W microwave irradiation for 5 min at 50 C in solvent-free medium under oxygen atmosphere. Biaryl products were extracted into organic phase using toluene-water extraction mixture (2:1 v:v). The organic phase containing the product was separated with a separatory funnel. To remove water remaining in the organic phase, a drying agent (MgSO4) was added into the organic phase. The anhydrous organic phase was subsequently evaporated to eliminate toluene. Finally, the biaryl compounds were dissolved in acetone and shipped to GS-MS analysis.
With anhydrous sodium carbonate; In water monomer; N,N-dimethyl-formamide; at 80℃; for 0.5h;Inert atmosphere; General procedure: The haloarene (1 mmol) and catalyst (0.2 mol%) were added to a dry Shlenk tube equipped with a magnetic stirring bar under nitrogen. To this was added DMF/H2O (1:1, 2 mL), sodium carbonate (2 mmol) and the boronic acid (1.4 mmol). The mixture was heated at 80 C for 30 min, then cooled to room temperature, diluted with acetone (3 mL) and filtered to remove the catalyst, base and unwanted salts. The % conversion was established using gas chromatography with reference to dodecane as an internal standard. Recycling was accomplished by washing the used catalyst with water (10 mL) then with DMF/H2O (1:1, 10 mL). The catalyst, usually somewhat discoloured, may then be used directly in the next coupling reaction with a substantial decrease in activity being observed.
91%Chromat. With palladium; potassium hydroxide; In water monomer; at 100℃; for 1h;Sealed tube; General procedure: The reaction was carried out in a sealed tube with spin bar consisting phenylboronic acid (0.146 g, 1.2 mmol), potassium hydroxide (0.112 g, 2 mmol), iodobenzene (0.206 g, 1 mmol) and PdNPs solution (50 L, 0.0005 mmol) in aqueous medium at 100 ◦C for 1 h with constant stirring (Scheme 2). The progress of the reaction was monitored using GC analysis (Perkin-Elmer, Clarus 400). After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was extracted with ethyl acetate for three times, dried over Na2SO4 and the solvent was evaporated under vacuum. The obtained crude product was then purified by column chromatography using silica gel, (100-200 mesh size) with petroleum ether/ethyl acetate (PE-EtOAc, 95:05) as eluent to give pure product. All the products are well known and were confirmed by GC-MS
97%Chromat. With potassium carbonate; In ethanol; water monomer; at 80℃; for 3h; General procedure: In a typical procedure, aryl halide (0.5 mmol), phenylboronic acid (0.75 mmol), K2CO3 (1.0 mmol), EtOH/H2O (v/v = 9:1, 5.0 mL) and catalyst (0.5 mol% Pd) were added in a 10 mL round bottom flask. The mixture was vigorously stirred at 80 C for required time under air atmosphere. After the completion of the reaction, the mixture was cooled to room temperature and filtered. The filtrate was extracted with ethyl acetate (2× 5 mL). The combined extracts were dried with Na2SO4, filtered and analyzed by GC (P.E. AutoSystem XL) or GC-MS (Agilent 6890 N/5973 N).
92%Spectr. With potassium carbonate; In water monomer; N,N-dimethyl-formamide; at 100℃; for 4h; General procedure: The efficiency of the designed nanocatalyst was verified in Suzuki cross-coupling reactions. General procedure for catalytic test using the nanocatalyst is as follows. Solvent dimethylformamide (DMF)/H2O (3:1), aryl halide (0.5 mmol),aryl boronic acid (0.6 mmol), K2CO3 (2 mmol), nanocatalyst(1 mol %), and a small stirring bar were added to a round bottom flask (25 mL). The flask containing reaction mixture was placed in an oil bath (100 C) and stirred under air atmosphere. After completion of reaction, the mixture was cooled to room temperature and the nanocatalyst was separated using a magnet. The separated nanocatalyst was washed several times with DMF. Finally the products wer eanalyzed by a gas chromatography mass spectrometer (GCMS).
93%Chromat. With potassium carbonate; In water monomer; N,N-dimethyl-formamide; at 100℃; for 1.5h; General procedure: Nanocomposite Pd catalyst (1 mol%) was added to a round-bottom flask (25 ml) and dispersed in dimethylformamide(DMF)/H2O (2:1) mixture. Then, aryl halide (0.5 mmol), aryl boronic acid (0.6 mmol), K2CO3(1.5 mmol), and a small stirring bar wereadded to the round-bottom flask. The flask containing reaction mixture was placed in an oil bath (100C) and stirred under airatmosphere. After completion of reaction, the mixture was cooled to room temperature and the nanocomposite Pd catalyst was separated using a magnet. The separated catalysts were washed severaltimes with DMF. Finally the products were analyzed by a GC-MS.
With anhydrous sodium carbonate; In ethanol; water monomer; at 80℃; for 2h;Catalytic behavior; Typically, halobenzene (0.5 mmol), benzene boronic acid (0.6 mmol), base (Na2CO3 or K2CO3) (1 mmol), catalyst (20 mg, 0.59 mol% Pd) and 6 mL of solvent [H2O, EtOH or H2O/EtOH (2:1, v/v)] were introduced into a round bottomed flask under stirring. The reaction was allowed to proceed at the desired reaction temperature for appropriate time. After reaction completion, the catalyst was separated by centrifuging and the obtained products were extracted with diethyl ether. The extracted phase was subjected to GC and GC massfor quantitative detection of products using toluene as the internal standard.
86%Chromat. With potassium carbonate; In water monomer; at 100℃; for 4h;Inert atmosphere; General procedure: A mixture of aryl halide (0.5 mmol, 1.0 equiv.), phenylboronic acid (0.6 mmol, 1.2 equiv.), K2CO3 (2 mmol, 4equiv.), the Pd-NP-PIL catalyst (1.7 mol% based on the arylhalide substrate) in water (3 mL) was heated to 100 C under nitrogen with vigorous stirring for 4 h. The reaction mixture was then cooled at r.t. and the product was extracted with diethyl ether (3×3 mL). The combined extracts were washed with brine (15 mL), dried over anhydrous MgSO4, filtered and the solution was analyzed by GC. The structure of the products was also confirmed by 1H NMR spectroscopy.

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  • 2
  • [ 615-37-2 ]
  • [ 71-43-2 ]
  • [ 643-58-3 ]
YieldReaction ConditionsOperation in experiment
60% General procedure: A 15mL glass vial equipped with magnetic stir bar was charged with 1mmol of aryl iodide substrate, arene (3mL, 67 equiv), tert-potassium butoxide (2 equiv), 35mg of IrPyBzASMNPs (0.42mol%) catalyst in 1mL DMSO, purged with nitrogen and sealed with rubber cap. Afterwards, the system was sonicated for 15min and irradiated with the 2×12W white LEDs by keeping at a distance of 10cm for 18h under constant stirring. After completion of the reaction, the catalyst was separated via external magnet and the supernatant was extracted with (3×30mL) ethyl acetate and water. Subsequently, the organic layer was collected, rotary evaporated and further purified by silica gel column chromatography using hexane.
54% With cesium hydroxide; 5,10,15,20-tetra(p-tolyl)porphyrin; tert-butyl alcohol; at 200℃; for 4h;Darkness; H2(ttp) (7.5 mg, 0.0112 mmol), 2-iodotoluene (28 μL, 0.224mmol), CsOH (335 mg, 2.24 mmol), tBuOH (210 μL, 2.24 mmol) were added inbenzene (2.0 mL, 22.4 mmol). The mixture was heated at 200 C for 4 h to afford54% 2-methylbiphenyl2 (2c).
54% With potassium 2-methylbutan-2-olate; N,N`-dimethylethylenediamine; at 80℃; for 24h;Inert atmosphere; General procedure: A Schlenk tube was charged with t-AmOK (1.5 mmol) under anatmosphere of nitrogen, and the solvent (toluene) was removedunder reduced pressure. Then 4-iodoanisole (117 mg, 0.5 mmol),ligand and benzene (4.0 mL) was added. The resulting mixture was stirred at 80 C for 24 h. After cooling to room temperature, the reaction mixture was quenched with water and extracted with ethyl acetate (10 mL3). The organic layers were combined, dried over Na2SO4 and concentrated under reduced pressure, and then purified by silica gel chromatograph (petroleum ether) to yield the desired product as a white solid.
51% With (5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate)cobalt(II); potassium hydroxide; tert-butyl alcohol; at 200℃; for 2h;Inert atmosphere; Darkness; CoII(t4-OMepp) (0.0112 mmol), aryl halide (0.224 mmol),KOH (2.24 mmol), tBuOH (2.24 mmol) were added in benzene (2.0 mL, 22.4 mmol).The mixture was degassed for three freeze-pump-thaw cycles and heated at 200 C. AfterGCMS analysis of reaction mixture to confirm complete consumption of aryl halide, thereaction mixture was distilled under reduced pressure at room temperature to remove the solvent. The crude residue was purified by column chromatography (silica gel, 230-400mesh) eluting with hexane to afford the biaryls (2).
20% With potassium tert-butylate; at 100℃; for 16h;Schlenk technique; Sealed tube; Irradiation; General procedure: Method A: in a glove box, a 25 mL Schlenk tube equipped with a stir bar was charged with aryl iodides (0.25 mmol),KOtBu (56 mg, 0.5 mmol), and benzene (2.0 mL) was added by syringe. Then the Schlenk tube was sealed by a Teflon screw cap and placed in an oil bath at 100 C (preheated to 100 C) with one 24 W CFL (approximately 5 cm away). The reaction mixture was allowed to stir for 16 h. After being cooled down, the solvent was removed in vacuo and the residue was purified by chromatography on silica gel (eluent:diethyl ether/petroleum ether) to provide the corresponding product. Method B: in a glove box, a 25 mL Schlenk tube equipped with a stir bar was charged with aryl iodides (0.25 mmol), bathophenanthroline (8.3 mg, 0.025 mmol), KOtBu(56 mg, 0.5 mmol), and benzene (2.0 mL) was added by syringe. Then the Schlenk tube was sealed by a Teflon screw cap and placed with one 24 W CFL (approximately 3 cm away). The reaction mixture was allowed to stir for36 h. Then the solvent was removed in vacuo and the residue was purified by chromatography on silica gel (eluent:diethyl ether/petroleum ether) to provide the corresponding product.
43%Chromat. With fullerene-C60; potassium hydroxide; tert-butyl alcohol; at 200℃; for 13h;Darkness; General procedure: C60 (0.00224 mmol), aryl halides (0.224 mmol), KOH(4.48 mmol), and tBuOH (2.24 mmol) were dissolved in benzene(2.0 mL, 22.4 mmol). The mixture was heated at 200 C. Afterconfirming the complete consumption of the aryl halide by GCeMSanalysis the solvent was removed by rotary evaporator. The cruderesidue was purified by column chromatography (silica gel,230e400 mesh) eluting with hexane to afford the correspondingbiaryls 1.
19%Chromat. With N1,N2-bis(4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl)ethane-1,2-diamine; potassium tert-butylate; at 120℃; for 24h;Sealed tube; General procedure: A reaction tube was charged with KOt-Bu (280.0 mg, 2.5 mmol) at room temperature, and then, 4-iodotoluene (109.0 mg, 0.5 mmol), fluorous ethylenediamine L (1170.0 mg, 1.5 mmol) and benzene (6.0 mL) were added. The resulting mixture was stirred at 120 C for 24 h in this sealed tube equipped with a Teflon plug. After cooling to room temperature, (the fluorous ligand can be recovered by extraction with perfluorotoluene 5 mL × 3, 91% recovery yield ) the reaction mixture was quenched and extracted with ethyl acetate (10 mL × 3). The organic layers were combined, dried over Na2SO4 and concentrated under reduced pressure, and then purified by silica gel chromatography (petroleum ether) to yield the desired product as a white solid (52.9 mg, 63% yield).

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  • 3
  • [ 932-31-0 ]
  • [ 1632-83-3 ]
  • [ 100-66-3 ]
  • [ 2622-63-1 ]
  • [ 643-58-3 ]
 

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