| 98% |
With cesium fluoride;Pd(dba)2; In toluene; |
Example 6 This is an example of Pd/ligand 1-catalyzed Suzuki reaction for biaryl synthesis. A reaction mixture of CsF (0.764 g, 5.06 mmol), 2-chlorobenzonitrile (0.307 g, 2.24 mmol), and p-tolueneboronic acid (0.329 g, 2.42 mmol), Pd(dba)2 (1 mg, 1.7 mumol), and ligand 1 (5 mg, 18 mumol) in toluene (4 mL) was heated at reflux and monitored by GC-MS. After 3.5 h, GC-MS analysis showed a >98% GC yield of the desired product 2-cyano-4'-methylbiphenyl. TON=1318 and TOF =377. |
| 98% |
With cesium fluoride;Pd(dba)2; In 1,4-dioxane; |
Example 7 This is an example of Pd/ligand 1-catalyzed Suzuki reaction for biaryl synthesis. A reaction mixture of CsF (0.764 g, 5.06 mmol), 2-chlorobenzonitrile (0.230 g, 1.68 mmol), and p-tolueneboronic acid (0.329 g, 2.42 mmol), Pd(dba)2 (2 mg, 3.4 mumol), and ligand 1 (5 mg, 18 mumol) in 1,4-dioxane (4 mL) was heated at reflux and monitored by GC-MS. After 8 h, GC-MS analysis showed a >98% GC yield of the desired product 2-cyano-4'-methylbiphenyl. TON=494 and TOF=62. |
| 95% |
With O4P(3-)*3K(1+)*5H2O; tris(1-adamantyl)phosphine; {2-[((acetyl-kappaO)amino)phenyl-kappaC](tri-1-adamantylphosphine)palladium}(p-toluenesulfonate); In tetrahydrofuran; at 100℃; for 0.166667h;Glovebox; |
A mixture of 2-chlorobenzonitrile (69 mg, 0.50 mmol, 1 equiv), 4-tolylboronic acid (75 mg, 0.55 mmol, 1.1 equiv), THF (100 jiL) were stirred into slurry, added K3P045H20 (0.33 g, 1.1 mmol, 2.2 equiv) then a THF stock solution of 3 and PAd3 (10 iL, 0.025 tmo1 Pd/PAd3). The reaction vial was capped then taken outside the glove box to an oil bath preset at 100 C for 10 mm. The reaction mixture was diluted with ethyl acetate then extracted with water. The combineorganic layers were evaporated and the crude product was purified by flash chromatography. After drying, 92 mg (95 %) of 7 was obtained as a colorless crystalline solid. NMR spectroscopic data agreed with literature values. |
| 92% |
With potassium phosphate;4-di-tert-butylphosphanyl-1,5-diphenyl-1H-[1,2,3]triazole; bis(dibenzylideneacetone)-palladium(0); In toluene; at 100℃; for 12h;Product distribution / selectivity; |
Example 7[0031] A Schlenk tube, which was flame-dried under vacuum and backfilled with nitrogen, was charged with boronic acid (1.5 mmol) and a base such as K3PO4 (2 equiv.)- The flask was evacuated and backfilled with nitrogen three times. Toluene (3 mL), a stock solution of a phosphine ligand (0.2 mol%) in toluene, a stock solution of Pd(dba)2 (0.1 mol%) in toluene, and aryl chloride (1.0 mmol) were subsequently added. The phosphine ligand was L1c as described in Example 5 above. The flask was sealed and the reaction mixture was heated to 100C with vigorous stirring for 12 hours. After cooling to room temperature, 10 mL of EtOAc was added and the mixture was washed with 10 mL of IN NaOH (aq.) and 10 mL of brine. The organic layer was dried over Na2SO4 and concentrated under reduced pressure. The crude product was purified by flash column chromatography on silica gel. The yields of the coupling reaction using phosphine ligand L1c coupled with catalyst Pd(dba)2 are summarized forth in Table 2 below |
| 92% |
With sodium carbonate; In ethanol; water; for 1h;Reflux; |
Ortho-chlorophenyl nitrile 1.376g (10mmol), the methyl boronic acid 1.700g (12.5mmol) and anhydrous sodium carbonate 2.764g (20mmol) a granulate, add 100mLEtOH/H2O (v/v, 1/1) in the three-neck bottle, heating to reflux, adding 41.4 mg polystyrene-triphenylphosphine-supported palladium catalyst, to continue heating reflux 1h, TLC detection reaction fluid neighbour chlorophenyl nitrile dematerialised, filtering, with 3×20 ml ethyl acetate wash, 2×4mlEtOH/H2O (v/v, 1/1) washing, drying at room temperature to constant weight, recovery of a polystyrene-triphenylphosphine-supported palladium catalyst 40.2 mg, recovery rate: 97% ; filtering the filtrate obtained by adding 40 ml of water, the organic phase (the upper) with 20 ml saturated salt water washing, washing of the organic reinforced with 2.0g a half hours drying by anhydrous sodium sulfate, concentrated, column chromatography separation, to obtain 2-cyano -4 the [...] -methyl biphenyl 1.78g, yield: 92%. |
| 87% |
With C21H28N2; potassium carbonate; palladium dichloride; In water; N,N-dimethyl-formamide; at 110℃; for 4h; |
General procedure: In a round bottle, ligand or palladium complexes (1 mol% mmol), aryl halides (1.0 mmol), arylboronic acid (1.2 mmol), K2CO3 (2.0 mmol) and 4 mL of DMF and 1 mL of H2O were added with a magnetic stir bar. The reaction mixture was carried out at the described 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 × 5mL) with Et2O. The organic layer was dried with anhydrous MgSO4, filtered and evaporated under vacuum. 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. |
| 81% |
With chloro-2,6-bis((sec-butylthio)methyl)pyridinepalladium(II) chloride; tetrabutylammomium bromide; potassium hydroxide; In water; at 120℃; for 3h;Inert atmosphere; Schlenk technique; Sealed tube; |
General procedure: A 50-mL Schlenk tube was charged with aryl halide (1.63 mmol), aryl boronic acid (2.61 mmol), KOH (3.26 mmol), complex 17d (0.5 mol %), TBAB (0.5 mol % relative to the aryl halide) and water (2 mL). The sealed mixture was stirred at 120 C until TLC analysis confirmed completion of the reaction (for GC analysis the products were extracted with toluene). The aqueous solution was then extracted with ethyl acetate (3 10 mL). The combined organic phases were dried over MgSO4, filtered and evaporated in vacuo. The residue product was purified by column chromatography on silica gel using a mixture of hexane and ethyl acetate as eluent to yield biaryls 23a-m: |
| 70% |
With N-methyliminodiacetic acid; potassium carbonate; palladium dichloride; In water; at 80℃; for 6h; |
The stirring method is added to the reaction vial 1.2mmol the methyl boronic acid, 1.0mmol O-chlorophenyl nitrile, 2.0mmolK2CO3, 6mlPEG400/H2O (v:v= 1:1), 0.02mmolPdCl2, 0.02mmol biligand N-methyl imine diethyla acid, stirring and heating in air to 80 C, reaction 6h. Terminate reaction with saturated sodium chloride, in the 0 C, using 6mol/LHCl adjusting pH= 2 by adding 10 ml toluene, stirring for ten minutes, separating, repetitive operation combining the two time phase, using saturated NaHCO3the solution and saturated NaCl solution 20 ml washing twice, after adding anhydrous sodium sulfate for drying, filtering, the filtrate recovered toluene. Sand smooth biphenyltetrazole crude product obtained.Crude product to evaporate toluene added in 6 ml anhydrous ethanol, heated to 80 C, cooling to room temperature, add 4, the 4 [...] -dimethyl biphenyltetrazole crystal seeds, in-5-0 C lower crystallization 12h, rapidly at the low temperature filter insoluble matter, the mother liquor removed in accordance with the above-mentioned operation the two time 4, the 4 [...] -dimethyl biphenyltetrazole by-product.After removing the by-product, to the resulting strawcoloured product adding 6 ml petroleum ether, heating to 50 C, natural cooling to room temperature, a small amount of bottom layer decadent oil object is dropped, at -25 C crystalline, low-temperature rapid filtration, the white solid obtained, purity > 99%, the method to achieve the total yield of 70%. |
|
With potassium fluoride;palladium diacetate; In para-xylene; water; ethylene glycol; dimethyl sulfoxide; toluene; |
Example 16 15 g of 2-chlorobenzonitrile, 15.8 g of p-tolueneboronic acid and 15.8 g of potassium fluoride were heated to 120 C. with 50 ml of p-xylene, 40 ml of glycol and 10 ml of water. At 80 C., a mixture of 24.7 mg of palladium acetate and 0.55 ml of TPPTS/H2 O solution (0.6 molar) in 2.5 ml of DMSO was added. After the reaction was complete, the phases were separated. The aqueous phase was washed with 50 ml of toluene. The combined organic phases were washed with 20 ml of water and subsequently dried over sodium sulfate. Crystallization from n-heptane gave 18.7 g of 2-cyano-4'-methylbiphenyl. |
|
With potassium fluoride;palladium diacetate; In para-xylene; water; dimethyl sulfoxide; glycerol; toluene; |
Example 15 15 g of 2-chlorobenzonitrile, 15.8 g of p-tolueneboronic acid and 15.8 g of potassium fluoride were heated to 120 C. with 50 ml of p-xylene, 40 ml of glycerol and 10 ml of water. At 80 C., a mixture of 24.7 mg of palladium acetate and 0.55 ml of TPPTS/H2 O solution (0.6 molar) in 2.5 ml of DMSO was added. After the reaction was complete, the phases were separated. The aqueous phase was washed with 50 ml of toluene. The combined organic phases were washed with 20 ml of water and subsequently dried over sodium sulfate. Crystallization from n-heptane gave 18.2 g of 2-cyano-4'-methylbiphenyl. |
|
With potassium fluoride;palladium diacetate; In para-xylene; water; dimethyl sulfoxide; toluene; diethylene glycol; |
Example 17 15 g of 2-chlorobenzonitrile, 14.8 g of p-tolueneboronic acid and 15.8 g of potassium fluoride are heated to 120 C. with 50 ml of p-xylene, 40 ml of diethylene glycol and 10 ml of water. At 80 C., a mixture of 24.7 mg of palladium acetate and 0.55 ml of TPPTS/H2 O solution (0.6 molar) in 2.5 ml of DMSO was added. After the reaction was complete, the phases were separated. The aqueous phase was washed with 50 ml of toluene. The combined organic phases were wahsed with 20 ml of water and subsequently dried over sodium sulfate. Crystallization from n-heptane gave 17.8 g of 2-cyano-4'-methylbiphenyl. |
|
With potassium fluoride;palladium diacetate; In para-xylene; water; dimethyl sulfoxide; toluene; 2,2'-[1,2-ethanediylbis(oxy)]bisethanol; |
Example 18 15 g of 2-chlorobenzonitrile, 14.8 g of p-tolueneboronic acid and 15.8 g of potassium fluoride were heated to 120 C. with 50 ml of p-xylene, 40 ml of triethylene glycol and 10 ml of water. At 80 C., a mixture of 24.7 mg of palladium acetate and 0.55 ml of TPPTS/H2 O solution (0.6 molar) in 2.5 ml of DMSO was added. After the reaction was complete, the phases were separated. The aqueous phase was washed with 50 ml of toluene. The combined organic phases were washed with 20 ml of water and subsequently dried over sodium sulfate. Crystallization from n-heptane gave 17.2 g of 2-cyano-4'-methylbiphenyl. |
|
With potassium fluoride;palladium(II) chloride; In para-xylene; water; dimethyl sulfoxide; glycerol; toluene; |
Example 27 15 g of 2-chlorobenzonitrile, 14.8 g of p-tolueneboronic acid and 15.8 g of potassium fluoride were heated to 120 C. with 50 ml of p-xylene, 40 ml of glycerol and 10 ml of water. At 80 C., a mixture of 38.66 mg of palladium(II) chloride and 1.1 ml of TPPTS/H2 O solution (0.6 molar) in 2.5 ml of DMSO was added. After the reaction was complete, the phases were separated. The aqueous phase was washed with 50 ml of toluene. The combined organic phases were washed with 20 ml of water and subsequently dried over sodium sulfate. Crystallization from n-heptane gave 18.9 g of 2-cyano-4'-methylbiphenyl. |
|
With potassium fluoride;palladium(II) chloride; In para-xylene; water; dimethyl sulfoxide; toluene; 2,2'-[1,2-ethanediylbis(oxy)]bisethanol; |
Example 30 15 g of 2-chlorobenzonitrile, 14.8 g of p-tolueneboronic acid and 15.8 g of potassium fluoride were heated to 120 C. with 50 ml of p-xylene, 40 ml of triethylene glycol and 10 ml of water. At 80 C., a mixture of 38.66 mg of palladium(II) chloride and 1.1 ml of TPPTS/H2 O solution (0.6 molar) in 2.5 ml of DMSO was added. After the reaction was complete, the phases were separated. The aqueous phase was washed with 50 ml of toluene. The combined organic phases were washed with 20 ml of water and subsequently dried over sodium sulfate. Crystallization from n-heptane gave 16.9 g of 2-cyano-4'-methylbiphenyl. |
|
With potassium fluoride; triethanolamine;palladium diacetate; In para-xylene; water; dimethyl sulfoxide; toluene; |
Example 20 15 g of chlorobenzonitrile, 14.8 g of p-tolueneboronic acid and 15.8 g of potassium fluoride were heated to 120 C. with 50 ml of p-xylene, 40 ml of triethanolamine and 10 ml of water. At 80 C., a mixture of 24.7 mg of palladium acetate and 0.55 ml of TPPTS/H2 O solution (0.6 molar) in 2,5 ml of DMSO was added. After the reaction was complete, the phases were separated. The aqueous phase was washed with 50 ml of toluene. The combined organic phases were washed with 20 ml of water and subsequently dried over sodium sulfate. Crystallization from n-heptane gave 17.2 g of 2-cyano-4'-methylbiphenyl. |
|
With potassium fluoride; triethanolamine;palladium(II) chloride; In para-xylene; water; dimethyl sulfoxide; toluene; |
Example 32 15 g of 2-chlorobenzonitrile, 14.8 g of p-tolueneboronic acid and 15.8 g of potassium fluoride were heated to 120 C. with 50 ml of p-xylene, 40 ml of triethanolamine and 10 ml of water. At 80 C., a mixture of 38.66 mg of palladium(II) chloride and 1.1 ml of TPPTS/H2 O solution (0.6 molar) in 2.5 ml of DMSO was added. After the reaction was complete, the phases were separated. The aqueous phase was washed with 50 ml of toluene. The combined organic phases were washed with 20 ml of water and subsequently dried over sodium sulfate. Crystallization from n-heptane gave 18.0 g of 2-cyano-4'-methylbiphenyl. |
|
With triethanolamine; sodium acetate; sodium carbonate;palladium(II) chloride; In para-xylene; water; dimethyl sulfoxide; toluene; |
Example 38 15 g of 2-chlorobenzonitrile, 14.8 g of p-tolueneboronic acid and 28.9 g of sodium carbonate were heated to 120 C. with 50 ml of p-xylene, 40 ml of triethanolamine and 10 ml of water. At 80 C., 19.3 mg of palladium chloride, 17.9 mg of sodium acetate and 0.55 ml of TPPTS/H2 O solution (0.6 molar) in 2.5 ml of DMSO were added. After the reaction was complete, the phases were separated. The aqueous phase was washed with 50 ml of toluene. The combined organic phases were washed with 20 ml of water and subsequently dried over sodium sulfate. Crystallization from n-heptane gave 17.8 g of 2-cyano-4'-methylbiphenyl. |
|
With triethanolamine; sodium carbonate;palladium diacetate; In para-xylene; water; dimethyl sulfoxide; toluene; |
Example 14 15 g of 2-chlorobenzonitrile, 14.8 g of p-tolueneboronic acid and 28.9 g of sodium carbonate were heated to 120 C. with 50 ml of p-xylene, 40 ml of triethanolamine and 10 ml of water. At 80 C., a mixture of 24.7 mg of palladium acetate and 0.55 ml of TPPTS/H2 O solution (0.6 molar) in 2.5 ml of DMSO was added. After the reaction was complete, the phases were separated. The aqueous phase was washed with 50 ml of toluene. The combined organic phases were washed with 20 ml of water and subsequently dried over sodium sulfate. Crystallization from n-heptane gave 17.8 g of 2-cyano-4'-methylbiphenyl. |
|
With sodium acetate; sodium carbonate;palladium(II) chloride; In 5,5-dimethyl-1,3-cyclohexadiene; para-xylene; water; dimethyl sulfoxide; |
Example 43 15 g of 2-chlorobenzonitrile, 14.8 g of p-tolueneboronic acid and 28.9 g of sodium carbonate were heated to 120 C. with 50 ml of p-xylene, 40 ml of DMSO and 10 ml of water. At 80 C., a mixture of 19.3 mg of palladium(II) chloride, 17.9 mg of sodium acetate and 0.55 ml of TPPTS/H2 O solution (0.6 molar) in 2.5 ml of DMSO was added. After the reaction was complete, the phases were separated. The aqueous phase was washed with 50 ml of xylene. The combined organic phases were washed with 20 ml of water and subsequently dried over sodium sulfate. The solvent was evaporated and the residue was crystallized from n-heptane. Yield: 18.8 g (89% of theory) of 2-cyano-4'-methylbiphenyl. |
|
With sodium acetate; sodium carbonate;palladium(II) chloride; In para-xylene; water; ethylene glycol; dimethyl sulfoxide; toluene; |
Example 33 15 g of 2-chlorobenzonitrile, 14.8 g of p-tolueneboronic acid and 28.9 g of sodium carbonate were heated to 120 C. with 50 ml of p-xylene, 40 ml of glycol and 10 ml of water. At 80 C., 19.3 mg of palladium chloride, 17.9 mg of sodium acetate and 0.55 ml of TPPTS/H2 O solution (0.6 molar) in 2.5 ml of DMSO were added. After the reaction was complete, the phases were separated. The aqueous phase was washed with 50 ml of toluene. The combined organic phases were washed with 20 ml of water and subsequently dried over sodium sulfate. Crystallization from n-heptane gave 18.7 g of 2-cyano-4'-methylbiphenyl. |
|
With sodium acetate; sodium carbonate;palladium(II) chloride; In para-xylene; water; dimethyl sulfoxide; glycerol; toluene; |
Example 34 15 g of 2-chlorobenzonitrile, 14.8 g of p-tolueneboronic acid and 28.9 g of sodium carbonate were heated to 120 C. with 50 ml p-xylene, 40 ml of glycerol and 10 ml of water. At 80 C., a mixture of 19.3 mg of palladium chloride, 17.9 mg sodium acetate and 0.55 ml of TPPTS/H2 O solution (0.6 molar) in 2.5 ml of DMSO was added. After the reaction was complete, the phases were separated. The aqueous phase was washed with 50 ml of toluene. The combined organic phases were washed with 20 ml of water and subsequently dried over sodium sulfate. Crystallization from n-heptane gave 18.3 g of 2-cyano-4'- methylbiphenyl. |
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