| 99% |
With potassium phosphate heptahydrate; [(2,6-(Ph2PO)C6H3(CHN(m-ClC6H4)))PdCl] In ethanol at 50℃; for 3h; |
|
| 99% |
With [C3H4ONC6H3CH2C3H3N2]PdCl; potassium carbonate In 1,4-dioxane at 110℃; for 7h; in air; |
|
| 99% |
With palladium diacetate; metformin hydrochloride; potassium carbonate In ethanol; water monomer at 80℃; for 0.583333h; Green chemistry; |
General procedure: To a 5 mL flask containing a mixture of Pd(OAc)2 (0.01 mmol, 0.025 g), Met.HCl (0.02 mmol, 0.033 mg), and K2CO3 (2 mmol, 276 mg) in distilled H2O (1.5 mL) and EtOH (99%, 1.5 ml) were added aryl halide (1 mmol) and boronic acid (1.1 mmol) at 80 C, and the mixture stirred for the appropriate amount of time (see Table 2). The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was washed with EtOAc (5Χ1ml) and the organic phase separated and evaporated. Further purification was by column chromatography (EtOAc/n-hexane) gave the desired coupled product. |
| 99% |
With potassium carbonate In ethanol; water monomer at 80℃; for 0.583333h; |
Suzuki-Miyaura coupling reaction
Suzuki-Miyaura coupling reaction;In a typical reaction, to a solution of 1 mmol of the aryl halide in 5 ml of water/ethanol (1:1) was added 1.1 mmol of phenyl boronic acid, 276 mg of K2CO3 (2 mmol) followed by 15 mg of the solid catalyst (1 mol%). The mixture was then stirred for the desired time at 80 °C. The reaction was monitored by thin layer chromatography (TLC). After completion of reaction, the reaction mixture was cooled to room temperature and the catalyst (SBA-15/Met/Pd(II)) was recovered by centrifuge and washed with ethyl acetate and ethanol.The combined organic layer was dried over anhydrous sodium sulfate and evaporated in a rotary evaporator under reduced pressure. The crude product was purified by column chromatography. |
| 99% |
With PdCl2(cyclohexyl-(1,1-diphenylprop-1-en-2-yl)phophine)2; potassium carbonate In tetrahydrofuran; water monomer; toluene at 40℃; for 15h; Inert atmosphere; |
|
| 99% |
With dichlorido-(N,N-diethyl-1-ferrocenyl-3-thiabutanamine)palladium(II); potassium carbonate In water monomer; N,N-dimethyl-formamide at 70℃; |
|
| 99% |
With potassium carbonate In water monomer at 25℃; for 26h; |
|
| 99% |
With sodium hydroxide In ethanol; water monomer at 70℃; for 0.5h; |
|
| 98% |
With Cs2CO3 In water monomer; N,N-dimethyl-formamide at 80℃; for 2h; |
|
| 98% |
With 1,2,4,5-[3-(2,6-(iPr)2C6H3)imidazol-1-yl-CH2]4-Ph(4+)*4Br(-); potassium carbonate In ethanol at 20℃; for 15h; |
|
| 98% |
With Br(1-)*C28H29BrN5O2Pd(1+); potassium carbonate In methanol; water monomer at 100℃; for 3h; |
|
| 98% |
With anhydrous sodium carbonate In propylene glycol; water monomer at 140℃; for 4h; Green chemistry; |
|
| 98% |
With trans-di(μ-acetato)bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II); potassium carbonate In water monomer for 4h; Sealed tube; Inert atmosphere; Reflux; |
|
| 98% |
With bis(acetonitrile)palladium(II) chloride; C10H11N3S; potassium carbonate In water monomer; N,N-dimethyl-formamide at 20℃; for 1h; Schlenk technique; Inert atmosphere; |
4.3. Representative procedure for the synthesis of compound 3aa
General procedure: An oven-dried Schlenk tube was charged with 2a (1.2 mmol), Pd(CH3CN)2Cl2 (0.1 mol%), L1(0.1 mol%), anhydrous K2CO3 (2 mmol).The Schlenk tube was backfilled with argon for three times. Then,DMF/H2O (2:1) (3 mL) was added by syringe, followed by additionof 1a (1 mmol) in a similar manner (solids were added with otherreagents before evacuation). The reaction was stirred in room temperatureand was monitored by TLC. After 1 h, the reaction mixturewas added water (50 mL), and then extracted with ethyl acetate(50 mL x 3). The combined organic layer was washed with brineand was dried over anhydrous Na2SO4. After filtered and concentratedunder reduced pressure, the residue was purified by columnchromatography on silica gel (Petroleum ether as eluent) to yieldthe product. |
| 97% |
With tetrabutylammonium bromide; anhydrous sodium carbonate In water monomer at 100℃; for 2h; |
|
| 97% |
With palladium diacetate; anhydrous sodium carbonate In water monomer; N,N-dimethyl-formamide at 35℃; for 0.5h; |
General procedure for the Suzuki reaction of aryl halide witharylboronic acids
General procedure: A mixture of aryl halide (1 mmol), arylboronic acid (1.5 mmol), Pd(OAc)2 (for aryl bromide 1 mol%, for aryl chloride 2 mol%), and Na2CO3 (2 mmol) was stirred in the mixture of H2O/DMF (3.5: 3 mL) at suitable temperature for indicated time in air. The reaction mixture was cooled to room temperature, and extracted by Et2O (10 mL) for three times. And then the organic phase was combined and evaporated under reduced pressure. The residue was purified on a silica gel (300-400 mesh) column to afford the desired product. |
| 97% |
With Pd(4,4'-bis(diphenylphosphino)-2,2',6,6'-tetra-methoxy-3,3'-bipyridine)Cl<SUB>2</SUB>; potassium hydroxide In ethanol; dichloromethane at 25℃; for 6h; |
|
| 97% |
With potassium phosphate tribasic trihydrate In ethanol; water monomer at 30℃; for 9h; |
|
| 96% |
With anhydrous sodium carbonate In ethanol; toluene at 100℃; for 20h; |
|
| 96% |
With C21H25ClN2Pd; potassium carbonate In toluene at 80℃; for 2h; |
|
| 96% |
With potassium carbonate In ethanol at 80℃; for 36h; Inert atmosphere; |
3-Methylbiphenyl (6aa)
General procedure: PICB-NHC-Pd catalyst (3) (0.000625 mmol, 0.25 mol% as Pd), K2CO3 (0.25 mmol, 1 eq.), boronic acid (0.3 mmol, 1.2eq.) and substrate (if it is solid, 0.25mmol, 1 eq.) were placed in reaction tube then heated and dried with dryer in vacuo for2~5 min. After Ar substitution with Ar balloon, substrate (if it is liquid, 0.25 mmol, 1 eq.) and EtOH were added. Reactionmixture was stirred at 80 C for 36 hours. Catalyst was seperated by filtration and washed with DCM (20 mL) and water.Aqueous NH4Cl solution (sat, 20 mL) was added and the aqueous layer was extracted with DCM (3 x 20 mL). Thecombined organic layers were dried over MgSO4 and the solvent was removed in vacuo. The residue was purified bypreparative TLC |
| 96% |
With potassium carbonate In ethanol; water monomer at 70℃; for 0.5h; Inert atmosphere; |
|
| 95% |
With N,N,N',N'-tetramethyl-N'',N''-didodecyl-guanidinium bromide; water monomer; palladium diacetate; potassium carbonate In ethanol at 110℃; for 12h; |
|
| 95% |
With C34H29ClN3O2PPd; tetrabutylammonium bromide; potassium carbonate In ethanol; water monomer at 20℃; for 12h; |
|
| 95% |
With palladium diacetate In 1,4-dioxane; water monomer at 110℃; for 3h; Inert atmosphere; Schlenk technique; Sealed tube; |
|
| 95% |
With tetrabutylammonium bromide In water monomer at 90℃; for 4h; Inert atmosphere; |
|
| 95% |
With palladium diacetate; potassium carbonate In ethanol; water monomer at 40℃; for 15h; Green chemistry; |
|
| 95% |
With potassium carbonate In ethanol; water monomer at 75℃; for 0.5h; Inert atmosphere; |
|
| 95% |
With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 0.166667h; |
2.9 General Procedure fortheSuzuki-MiyauraCross-Coupling Reaction Using Fe3O4(at)MCM-41-SB-Pd asCatalyst
General procedure: 2 mg of the nano-catalyst (Fe3O4MCM-41-SB-Pd)was dispersed in DMF (5 mL) using sonication for30min at room temperature. Then, aryl halide (1mmol), phenylboronic acid (1.2mmol) and K2CO3(1.2mmol) wereadded to the reaction flask and the mixture was refluxed at120°C. The progress of the reaction was checked by TLC(n-hexane/EtOAc). After completion of the reaction, thereaction mixture was cooled to the room temperature. Thecatalyst was separated by an external magnet and washedwith ethyl acetate. The resultant mixture was extracted withn-hexane to isolate the product and then the crude productwas recrystalized from n-hexane. |
| 95.6% |
With potassium phosphate tribasic trihydrate In ethanol; water monomer at 20℃; for 8h; Irradiation; |
|
| 95% |
With Sodium hydrogenocarbonate In water monomer at 20℃; for 5h; Green chemistry; |
4.2. General procedure for Pd(at)OC-MA catalysted Suzuki-Miyaura coupling reactions
General procedure: In a representative experiment, Pd(at)OC-MA catalyst (3 mg) was added to a mixture of bromobenzene (0.1 mmol), aryl boronic acid (0.15 mmol) and NaHCO3 (0.15 mmol) in H2O (3 mL), and the reaction mixture was stirred vigorously at room temperature for 5 h. After the reaction, it was extracted with CH3COOC2H5 and monitored by TLC analysis. The catalyst was recovered by high-speed centrifugation and then washed with H2O (3 × 3 mL) and CH3COOC2H5 (3 × 3 mL) and dried at 60 °C for 8 h for the next run. Also, the organic components were concentrated on a rotary evaporator to give the desired biaryl product. The homologous product was obtained by flash chromatography and analyzed by NMR. |
| 95% |
With palladium diacetate; (1s,5s)-9-([1,1'-biphenyl]-2-yl)-9-phosphabicyclo-[3.3.1]nonane; potassium hydroxide In tetrahydrofuran; methanol at 25℃; for 12h; Inert atmosphere; Schlenk technique; Sealed tube; |
|
| 94% |
With anhydrous sodium carbonate at 100℃; for 0.5h; Heating; |
|
| 94% |
With Pd/C; potassium carbonate In water monomer; N,N-dimethyl-formamide at 40℃; for 5h; |
Suzuki Cross-Coupling Reactions of Aryl Bromides; GeneralProcedure
General procedure: To a tube equipped with a magnetic stir bar were added catalyst 1(7.0 mg, 0.1 mol% Pd), K2CO3 (138 mg, 2.0 equiv), arylboronicacid (1.1 equiv), and aryl bromide (0.5 mmol) in turn. Subsequently,the solvent (DMF-H2O, 3:2, 2.0 mL, v/v) was added under an airatmosphere. The reaction was then heated to 40 °C and stirred untilthe aryl bromide was completely consumed as determined by TLC.After completion of the reaction, the reaction mixture was purifiedby silica gel column chromatography to afford the desired pureproduct. |
| 94% |
With potassium carbonate In ethanol; water monomer at 75℃; for 1h; Inert atmosphere; |
|
| 94% |
With potassium carbonate In ethanol at 40℃; for 3h; |
|
| 93% |
With potassium carbonate In water monomer; N,N-dimethyl-formamide at 80℃; for 2h; Schlenk technique; |
2.4. catalytic performance for suzuki cross coupling reactions
General procedure: In the Suzuki cross coupling reactions, a mixture of phenyl-boronic acid (0.6 mmol, 1.2 equiv), aryl halide (0.5 mmol, 1 equiv),K2CO3(1 mmol, 2 equiv), and Pd-Cu NWs (4 mg) were placedin a Schlenk tube (10 mL), which contained 2 mL of N,N-dimethylformamide (DMF) and water (H2O) (v/v = 1/1). Themixture was then stirred for a desired period of time at a selectedtemperature, and the reaction was monitored by thin layer chro-matography (TLC). Afterward, the reaction mixture was cooleddown to room temperature. And the catalyst was recovered byfiltration, followed by washing thoroughly with ethyl acetate andwater. The combined organic layer was dried by Na2SO4, and thefiltered residue was purified by flash column chromatography onsilica gel. As for the recycling experiments, we conducted severalparallel experiments under identical conditions and recycled thecatalyst for next run test. The target reactions would get supple-ment of catalysts from the other parallel experiments to make surethe scale of catalyst with 4 mg. |
| 93% |
With potassium carbonate In ethanol; water monomer for 0.833333h; Sonication; |
2.3. General procedure for the Suzuki-Miyaura coupling reaction
General procedure: A vial equipped with a magnetic stirrer bar and a condenser was charged with aryl halide (1 mmol), phenylboronic acid (1.2 mmol),K2CO3 (2 mmol), catalyst (8 mol% Ni) and Water/EtOH (1:1) (4 mL)and the reaction mixture was irradiated in ultrasonic apparatus. The reaction progress was followed using thin layer chromatography. After completion of the reaction, the mixture was cooled to room temperature,the catalyst was separated by an external magnet, and the product was extracted with ethyl acetate (15 mL) and dried over anhydrous MgSO4. The resulting solution was evaporated under vacuum to givethe crude product. The separation of product by column chromatography on silica gel using n-hexane or different mixtures of n-hexane,ethyl acetate as the eluents to afford the highly pure products (Table 4). The obtained pure products were characterized by physical methods and the IR, 1H NMR and 13C NMR spectra. |
| 93% |
With potassium carbonate In water monomer; N,N-dimethyl-formamide at 80℃; for 0.25h; |
|
| 93% |
With sodium hydroxide In ethanol; water monomer at 60℃; for 1h; |
|
| 93% |
With [Ir(2-phenylquinoline)2(2,2'-bipyrimidine)PdCl2](PF6); Cs2CO3; triphenylphosphine In ethanol; 1,2-dichloro-ethane at 20℃; for 8h; Inert atmosphere; Schlenk technique; Irradiation; |
|
| 92% |
With potassium carbonate In N,N-dimethyl-formamide at 150℃; for 0.5h; microwave irradiation; |
|
| 92% |
With potassium carbonate In N,N-dimethyl acetamide at 100℃; for 6h; |
|
| 92% |
With potassium carbonate In water monomer at 25℃; for 3h; |
|
| 92% |
With tripotassium phosphate tribasic; (NC5H3(N2C7H4(CH2)3CH3)2)NiBr(1+)*Br(1-)=Ni(NC5H3(N2C7H4(CH2)3CH3)2)Br2; triphenylphosphine In 1,4-dioxane at 100℃; for 24h; |
|
| 92% |
With potassium carbonate In water monomer; acetone at 75℃; for 11h; Green chemistry; |
|
| 92% |
With tetrabutylammonium bromide In water monomer at 90℃; for 1h; Inert atmosphere; Green chemistry; |
|
| 92% |
With potassium carbonate In ethanol; water monomer at 100℃; for 2.08333h; Green chemistry; |
2.3. General procedure for the Suzuki-Miyaura coupling reaction
General procedure: A vial equipped with a magnetic stirrer bar and a condenser wascharged with aryl halide (1 mmol), phenylboronic acid (1.2 mmol),K2CO3 (2 mmol), catalyst (12 mg Ni complex) and Water/EtOH (1:1)(4 mL) and the reaction mixture was heated in 100 °C. The reactionprogress was followed using thin layer chromatography. After completionof the reaction, the mixture was cooled to room temperature,the catalyst was separated by an external magnet, and theproduct was extracted with ethyl acetate (15 mL) and dried overanhydrous MgSO4. The resulting solution was evaporated undervacuum to give the crude product. The separation of product by columnchromatography on silica gel using n-hexane or different mixturesof n-hexane, ethyl acetate as the eluents to afford the highlypure product (Table 4). The obtained pure products were characterizedby melting points and IR and 1H NMR spectra. |
| 92% |
With tripotassium phosphate tribasic; C18H16ClN3PdS; tetrabutylammonium bromide In N,N-dimethyl acetamide; water monomer at 96℃; for 1.5h; Irradiation; |
|
| 92% |
With C16H18I2N3O3PPd; potassium carbonate In water monomer; isopropanol at 60℃; for 1h; Inert atmosphere; |
2.6. Typical procedure for Suzuki-Miyaura cross-coupling reaction
General procedure: 0.24 mmol of the aryl boronic acid and 0.2 mmol of aryl bromide were dissolved in 4 mL isopropanol-water (3:1) solution. To the above solution, 0.4 mmol of potassium carbonate and 0.001 mmol of catalyst (0.5 mol%) were added and the reaction mixture was stirred under heating condition in a preheated oil bath at 60 °C for variable time as mentioned in the Table 2 . The progress of the reaction was monitored by using thin layer chromatography. After completion of the reaction, all solvent were removed under reduced pressure. The product was extracted by using hexane and dried over Na2SO4 . Yields were determined from GC-MS. To investigate the role of the solvents and the base used in the reaction mixture, test has been carried out using different solvents and bases. It has been found that the use of isopropanol-water (3:1) as solvent and K2CO3 as base at 60 °C condition gives the maximum yield under N2 atmosphere. |
| 91% |
With bis(1,3,7,9-tetramethylxanthine-8-ylidene)palladium diiodide; potassium hydroxide In water monomer at 65℃; for 6h; Inert atmosphere; |
|
| 90% |
With potassium fluoride In N,N-dimethyl-formamide at 100℃; for 4.5h; Inert atmosphere; |
|
| 90% |
With C31H26N6O4Pd; potassium carbonate In water monomer at 100℃; for 2h; |
|
| 90% |
With C28H40Br4N4Pd2; potassium carbonate In water monomer; acetone at 20℃; for 1h; |
4.3 General procedure of Suzuki reaction
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. |
| 90.5% |
With [2-(2-oxazoliny)-6-(2-pyridyl)]phenylpalladium(II) chloride; potassium carbonate In 1,4-dioxane at 60℃; for 10h; |
|
| 90.3% |
With C36H33N2O5PPd; anhydrous sodium carbonate In methanol at 85℃; for 2h; |
2.3 General protocol for the Suzuki reaction
General procedure: A round bottom flask was charged with the aryl halide (0.5mmol), phenylboronic acid (0.75mmol), base (1.5 or 3mmol), catalyst (0.01mmol) and solvent (7mL), although the amount of the reagents and catalysts was diminished to half when catalysts 2-4 were utilized. The mixtures were heated for the times 2, 4, 8 and 24h and at the temperatures 85 and 100°C given in the tables using the bases and catalysts there indicated. The products were characterized by GC. |
| 90% |
With anhydrous sodium carbonate In ethanol; water monomer for 20h; Reflux; |
|
| 90% |
With potassium phosphate tribasic trihydrate; hydrogen In water monomer at 40℃; for 9h; |
|
| 89% |
With palladium diacetate; Cs2CO3; 1,3-bis(4,5-dihydrooxazol-2-yl)benzene In 1,4-dioxane at 80℃; for 4h; |
|
| 89% |
With tripotassium phosphate tribasic; [Pd2(3,4-dichloroacetophenone thiosemicarbazone)2(bis(diphenylphosphino)ferrocene)] In N,N-dimethyl-formamide at 130℃; for 36h; Inert atmosphere; Schlenk technique; |
General procedure for Suzuki-Miyaura reactions
General procedure: A Schlenk tube was charged with aryl boronic acid (0.4 mmol), K3PO4 (0.6 mmol), and the complex IV (0.5 mol %). The tube was connected to a vacuum line under argon and purged three times. N,N-dimethylformamide (2 mL) and aryl halide (0.3 mmol) were added. The reaction mixture was stirred at 130 °C between 24-48 h. At the end of the reaction, the reaction mixture was cooled to room temperature, diluted with diethyl ether, and washed with water. The combined organic phase was dried over anhydrous Na2SO4. After removal of the solvent, the residue was subjected to column chromatography on silica gel using ethyl acetate and petroleum ether mixtures to afford the Suzuki-Miyaura product in high purity. |
| 89% |
With sodium hydroxide In N,N-dimethyl-formamide at 130℃; for 0.216667h; Schlenk technique; |
|
| 88% |
With tri-tert-butyl(decyl)phosphonium tetrafluoroborate; palladium diacetate; Cs2CO3 In toluene at 30℃; for 12h; Inert atmosphere; Schlenk technique; |
|
| 88% |
With tetrabutylammonium bromide; potassium carbonate In water monomer at 80℃; for 4h; |
|
| 87% |
With potassium carbonate In ethanol at 20℃; for 4h; in air; |
|
| 87% |
With potassium carbonate In N,N-dimethyl-formamide at 110℃; for 3h; |
|
| 86% |
With potassium carbonate In ethanol; water monomer at 20℃; for 10h; |
|
| 86% |
With anhydrous sodium carbonate In ethanol; water monomer at 140℃; for 0.133333h; Microwave irradiation; |
|
| 86% |
With (2-methoxyphenyl)diphenylphosphine; palladium diacetate; Cs2CO3 In 1,4-dioxane at 100℃; for 5h; Inert atmosphere; Schlenk technique; |
4.3. General procedure for the palladiumcatalyzedSuzuki-Miyaura cross-couplingreactions
General procedure: In a Schlenk tube, in an inert atmosphere, a solutionof [Pd(OAc)2] in 1,4-dioxane, a solution ofthe ligand 1 (ratio Pd/1 1/1) in 1,4-dioxane, arylhalide (0.5 mmol), aryl boronic acid (0.75 mmol),Cs2CO3 (0.325 g, 0.75 mmol), decane (0.025 mL, internalreference) and a complementary amount of1,4-dioxane, so that the total reaction volume was2.0 mL, were introduced. The reaction mixture wasthen heated at 100 °C. After cooling to room temperature,a small amount (0.5 mL) of the resulting solutionwas passed through a Millipore filter and analyzedby GC. |
| 85% |
With potassium carbonate In ethanol; water monomer at 80℃; for 1.16667h; |
2.2 Suzuki coupling reaction
General procedure: General procedure: Aryl halide (1.0 mmol), arylboronic acid (1.2 mmol), base (2.5 mmol), and Fe3O4/SiO2-Met-Pd(OAc)2 (10 mg, 0.14 mol% Pd) were added to the vessel (10 mL) with 3 mL of solvent. The mixture was continuously stirred at 80 °C in an air atmosphere for the desired time until complete consumption of the starting aryl halide as monitored by TLC. After magnetic separation of the catalyst, the product was extracted with diethyl ether and purified by column chromatography (n-hexane: chloroform). In the recycling experiment, the separated catalyst was then washed with ether and dried under vacuum to remove residual solvent |
| 84% |
With potassium carbonate In ethanol; water monomer at 100℃; for 8h; Inert atmosphere; |
|
| 84% |
With C32H38N7Pd(1+)*Br(1-); potassium carbonate In water monomer; N,N-dimethyl-formamide at 100℃; for 20h; |
|
| 84% |
With tetrabutylammonium bromide; potassium carbonate In water monomer at 90℃; for 6h; Green chemistry; |
Procedure for cross coupling of 4-iodoanisole and phenylboronic acid using GO-PMMA-Pd catalyst
General procedure: 25-ml RB was charged with 4-iodo anisole (1.0 mmol), phenyl boronic acid (1.5 mmol), GO-PMMA-Pd catalyst (0.3 mol %), K2CO3 (1 mmol), TBAB (10 mol %) and 2 ml water. The mixture was allowed to stir at 90 °C for an appropriate time (Table 1) and the extent of the reaction was monitored by thin layer chromatography (TLC). After the completion of the reaction, the reaction mixture was extracted by ethyl acetate (2×25 mL) and washed with water repeatedly. The catalyst was filtered off and washed several times with ether and water (1:1) until no significant product was obtained in the wash. The recoverd catalyst was reused for the next coupling experiment. The reaction mixture was dried over anhydrous Na2SO4, concentrated in vacuum and purified by column chromatography on silica gel 60-120 mesh using petroleum ether as eluent to obtain pure product. The catalyst recoverd after 5th run was subjected to ICP-AES for Pd content analysis. The isolated products were analysed by 1H NMR and 13C NMR spectroscopy. |
| 84% |
With anhydrous Sodium acetate In water monomer |
2.2. General experimental procedures for Suzuki couplings reaction
General procedure: In a representative experiment, FS-PdCl 2 catalyst (15 mg) wasadded to mixture of bromobenzene (0.4 mmol, 62.8 mg), arylboronicacid (0.6 mmol, 73.6 mg), NaOAc (0.6 mmol, 49.2 mg)in H 2 O (15 mL), and the reaction mixture was stirred vigorouslyat 60 °C for 10 hours. After the reaction, it was extracted withCH 3 COOC 2 H 5 and monitored by TLC analysis. The catalyst was detachedby high speed centrifugation and then washed with H 2 O(3 × 3 mL) and CH 3 COOC 2 H 5 (3 × 3 mL), and dried at 70 °C for 8h for the next run. Furthermore, the organic component were concentratedon a rotary evaporator to give the desired biaryl group.The homologous product were obtained by flash chromatography. |
| 81% |
With potassium carbonate In 1-methyl-pyrrolidin-2-one at 90℃; for 2.5h; |
|
| 80% |
With potassium carbonate In ethanol at 78℃; for 1h; |
2.2 Typical Procedure for the Suzuki-Miyaura-Coupling
General procedure: An Agilent 6890 N-GC-5973 N-MSD chromatograph,using a 30 m x 0.25 mm Restek, Rtx-5SILMS columnwith a film layer of 0.25 μm was used for GC-MSmeasurements. The temperature of the injector was250 °C. The initial temperature of column was 45 °C for1 min, followed by programming at 10 °C/min up to310 °C and a final period at 310 °C (isothermal) for17 min. The carrier gas was He and the operation modewas splitless. 1H NMR spectra were made on BRUKER Avance-300instrument using TMS as internal standard in CDCl3. Before the reaction, the catalyst was treated at 120 °Cfor 1 h. Iodobenzene (1 mmol), phenylboronic acid(1.5 mmol), the pretreated catalyst (0.1 g) and potassiumcarbonate (3 mmol) were stirred for 1 h in refluxing ethanol(5 ml). Then the solid was separated by filtration, andthen washed by ethanol. The solvent was evaporated. Theresidue was subjected three times to extraction withdichloromethane-water. Anhydrous sodium sulphate wasused to eliminate the residual water from the organic phase,then it was filtered and the solvent was evaporated. Theproduct’s structure was verified by 1H NMR and/or GC-MS analysis. The catalyst was recovered by washing withethanol and drying at 120 °C for 1 h before reuse. 1,1'-Biphenyl was isolated as white powder. 1H NMR(300 MHz, CDCl3) δ (ppm): 7.61-7.58 (d, 4H); 7.46-7.41(dd, 4H); 7.37-7.34 (d, 2H);. GC: Rt: 12.101 min. MS (m/z): 154 (M+), 128, 115, 102, 76. 4-Methyl-1,1'-biphenylwas isolated as white solid. 1H NMR (300 MHz, CDCl3) δ(ppm): 2.39 (s, 3H), 7.23-7.26 (m, 2H), 7.32-7.34 (t, 1H),7.40-7.44 (t, 2H), 7.48-7.51 (d, 2H), 7.56-7.59 (d, 2H).3-Methyl-1,1'-biphenyl was isolated as yellow liquid. 1HNMR (300 MHz, CDCl3) δ (ppm): 2.39 (s, 3H), 7.13-7.14(d, 1H), 7.29-7.32 (t, 2H), 7.37-7.41 (m, 4H), 7.55-7.57(d, 2H). 2-Trifluoromethyl-1,1'-biphenyl was isolated aslight yellow liquid. 1H NMR (300 MHz, CDCl3) δ (ppm):7.30-7.44 (m, 7H), 7.49-7.54 (t, 1H), 7.71-7.74 (d, 1H). |
| 80% |
With potassium carbonate In water monomer for 10h; Reflux; |
|
| 80% |
With C70H48N6O2Pd; sodium lauryl sulfate; potassium carbonate In water monomer at 20℃; Green chemistry; |
|
| 77% |
With tripotassium phosphate monohydrate In water monomer; toluene at 100℃; for 1.5h; |
|
| 77% |
With triethylamine at 110℃; for 1h; Ionic liquid; Inert atmosphere; Green chemistry; |
General procedures for the Suzuki reaction
General procedure: Aliquots of 1.0 mmol aryl halide, 3.0 mL of the catalytic dispersion and 3.0 mL[emim] [BF4] were added to a screw-capped vial with a side tube. The mixture was degassed under nitrogen purge for 10 min at room temperature, then slowly heated to 110 °C with vigorous stirring for 0.5 h to activate the reactants, as described elsewhere [35]. Next, the mixture was cooled to room temperature. Then, then 0.18 g phenylboronic acid (1.5 mmol) and, 0.40 mL NEt3 (3.0 mmol) were added. The mixture was again degassed under nitrogen purge for 10 min.,after which the vial was bathed in preheated oil at a set temperature and magnetically stirred under nitrogen. After the reaction was complete, the mixture was cooled to room temperature rapidly. Using diethyl ether (3 × 20 mL), the product was extracted from the reaction mixture, then washed with water. The organic phase was collected, concentrated, and the subsequent product dried under vacuum at 40 °C, before weighing and analysis by 1H NMR. |
| 76% |
With anhydrous sodium carbonate In ethanol; water monomer at 60℃; for 4h; |
|
| 76% |
With C41H43Cl2N4PPd; Cs2CO3 In 1,2-dimethoxyethane at 100℃; for 2.5h; Glovebox; Inert atmosphere; Sealed tube; |
|
| 75% |
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 16h; |
|
| 75% |
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 6h; |
2.7 General procedure for Suzuki coupling reaction
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 80°C for an appropriate time. After completion of the reaction, the procedure was followed as outlined in Section 2.6. |
| 75% |
With potassium carbonate In neat (no solvent) at 50℃; for 0.0666667h; Microwave irradiation; |
2.9. General synthesis of Suzuki coupling reactions
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 50°C 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. |
| 75% |
With potassium carbonate In neat (no solvent) for 0.1h; Schlenk technique; Microwave irradiation; |
2.6. General fabrication of biaryls using Pd NPsSch-boehmiteunder solvent-free conditions
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. |
| 74% |
With anhydrous sodium carbonate In N,N-dimethyl-formamide at 50℃; for 12h; |
|
| 74% |
With Pd(CN(2,6-(2,6-(i-Pr)<SUB>2</SUB>C<SUB>6</SUB>H<SUB>3</SUB>)<SUB>2</SUB>C<SUB>6</SUB>H<SUB>3</SUB>))<SUB>2</SUB>; sodium tertiary butoxide In isopropanol at 20℃; for 8h; Inert atmosphere; Schlenk technique; Glovebox; Sealed tube; |
|
| 74% |
With palladium nanoparticles supported on Fe3O4 loaded Schiff base modified kaolin In neat (no solvent) for 0.1h; Alkaline conditions; Microwave irradiation; Green chemistry; |
2.4. General procedure for Suzuki coupling reactions
General procedure: The mixture containing Pd NPsKao/Fe3O4/Pyr (0.025 mol %), arylhalide (1 mmol), Na2CO3 (3.5 mmol) and phenyl boronic acid (1.8mmol) was subjected to microwave irradiation for 6 min. Upon thecompletion of the reaction, the mixture was extracted with water:toluene (1:2) three times. The organic phase containing biaryls wasevaporated and the product was characterized by GC/MS analysis. |
| 73% |
With potassium carbonate at 50℃; for 0.0833333h; Schlenk technique; Microwave irradiation; |
2.2.4. General procedure for Suzuki coupling reactions
General procedure: Firstly, the coupling reaction of 4-bromoanisol and phenylboronicacid was determined as the model reaction. Then, to detectideal reaction conditions, the effects of base system, reaction time,and catalyst amount on the yield of the biaryl compounds wereinvestigated for the model coupling reaction which occurred in thepresence of the synthesized P (4-PMB)-Pd (II) catalyst.As a result of the determined optimum conditions, several arylhalides (1.12 mmol), phenyl boronic acid (1.87 mmol), potassiumcarbonate (3.75 mmol), and P (4-PMB)-Pd catalyst (0.01 mol%) wereput into a Schlenk tube and mixed. The reactions were actualizedby microwave irradiation technique using 400W power in solventlessmedia for 5 min. At the end of the coupling reactions,toluene (4 mL) was added on the obtained products and filtered.Then, extraction of the supernatant was done with water (2 mL) forthree times, and the organic phase, which contained synthesizedbiaryl compound, was separated from water using separatoryfunnel. To remove the water completely, MgSO4 was added on theorganic phase. Then, toluene was removed at room temperature, and the yield of biaryl compound which was completely dried wascalculated. To verify the structures of the biaryl compounds, theywere analyzed by GC/MS technique. |
| 72% |
With tripotassium phosphate tribasic In water monomer at 60℃; for 3h; |
|
| 71% |
With Cs2CO3 In tetrahydrofuran at 80℃; for 12h; |
|
| 71% |
With potassium carbonate In water monomer at 80℃; for 6h; |
|
| 70% |
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 3.5h; |
|
| 70% |
With Pd/CoFe2O4; anhydrous sodium carbonate In ethanol for 12h; Reflux; |
|
| 70% |
With C23H35N4O4Pd(1+)*Br(1-); potassium carbonate In water monomer at 100℃; for 1h; |
|
| 69% |
With Cs2CO3 In water monomer; N,N-dimethyl-formamide at 30℃; for 24h; Irradiation; |
2.3. Photocatalytic reactions
General procedure: The reactions were conducted under an air atmosphere with apressure of 1 atm. When aryl bromides were used as substrates,the reactant mixture consisted of 1 mmol of aryl bromide, 2 mmolof phenylboronic acid, 3 mmol of Cs2CO3, 50 mg of Pd(at)NiO80/SiC,7 mL of dimethylformamide (DMF) and 3 mL of H2O. When arylchlorides were used as substrates, the reactant mixture consistedof 1 mmol of aryl chloride, 2 mmol of phenylboronic acid, 3 mmolof NaOH, 2 mmol of cetyltrimethylammonium bromide (CTAB),100 mg of Pd(at)NiO80/SiC and 10 mL of H2O. The reaction temperaturewas set at 30 °C and controlled by a circulating water bath.The mixture was stirred at 500 rpm using a magnetic stirrer during the reaction and was exposed to a xenon lamp. A low-pass optical filter was employed to block light with k < 400 nm. The light intensity was maintained at 0.35 W/cm2 for both aryl bromides and arylchlorides. The effect of the wavelength of light on catalytic performance was investigated using various light-emitting diode (LED)lamps with different wavelengths.After reaction, the reaction mixture was diluted with dichloromethane(DCM, 10 mL). The organic phase was extracted and filtered through a millipore filter (pore size: 0.22 lm). Then,0.5 mmol of n-dodecane was added as an internal standard. The product yield was determined by gas chromatography-mass spectrometry(GC-MS, BRUKER SCION SQ 456 GC-MS) using ndodecaneas the internal calibration standard. The values givenare the average of two experiments. The yields were calculated based on the amount of aryl halide. The residue was purified bycolumn chromatography on silica gel (silica: 200-300; eluant: hexane/ethyl acetate) to isolate the desired product. |
| 68% |
With 3,5-di-tert-butyl-2-hydroxybenzaldehyde; potassium carbonate; palladium (II) chloride In ethanol; water monomer at 20℃; for 2h; |
General procedure for Suzuki-Miyaura reaction
General procedure: To a round bottle with a magnetic stir bar, ligand (0.01% mmol), PdCl2 (0.01% mmol), aryl halides (1.0 mmol), phenylboronic acid (1.2 mmol), K2CO3 (2.0 mmol) and 6 ml of solvent were added. The reaction mixture was conducted at room temperature for the required time, and then the solvent was removed under reduced pressure. The residual was diluted with Et2O (5 mL), followed by extraction twice (2×5 mL) with Et2O. The organic layer was dried with anhydrous MgSO4, filtered and evaporated under vacuum. The conversions rates were analyzed by gas chromatography, based on the peak area normalization method. The corrected factor was determined by samples against a standard of n-heptane. The crude products were purified by silica-gel column chromatography using petroleum ether-ethyl acetate (20:1) as an eluent, and the isolated yield was then calculated based on the feeding of the aryl halide. The isolated corresponding products were characterized by 1H NMR and 13C NMR. |
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