(2-phenylphenyl)boronic acid

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of 4-bromoindole (1 g, 5 mmol), and 2-biphenylboronic acid (1 g, 5 mmol) in THF (17 mL) were added Palladium catalyst Pd(PPh3)4 (0.2 g, 0.17 mmol) and the freshly prepared sodium hydroxide solution (0.6 g, 15 mmol in 7 mL of water). The system was degassed and then charged with nitrogen. The degas procedure was repeated for three times. The mixture was stirred under nitrogen at 75° C. oil bath for overnight. TLC showed the completion of the coupling reaction. The mixture was cooled to room temperature, diluted with ethyl acetate, and separated from water layer. The ethyl acetate solution was washed with brine, and dried over Na2SO4. After filtration, the solvents were evaporated, and the crude product was purified on a silica gel column to give 1.26 g (93%) of 4-biphenyl-2-yl-1H-indole. The system was degassed charged with nitrogen the completion of the coupling reaction The mixture was cooled to room temperature separated from water layer The ethyl acetate solution was washed with brine dried over Na2SO4 After filtration the solvents were evaporated the crude product was purified on a silica gel column

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of compound 4 (40 g, 205 mmol, 1 equiv), (biphenyl-2-yl)boronic acid (81.2 g, 410 mmol, 2 equiv), powdered potassium carbonate (85 g, 615 mmol, 3 equiv), and bis(triphenylphosphine)palladium(II)dichloride (7.2 g, 10.3 mmol, 0.05 equiv), 1,4-dioxane (300 mL) and water (150 mL) was heated overnight at 80° C. The reaction was poured into 500 mL of water and extracted with ethyl acetate (3×400 mL). The combined organic layers were washed with saturated brine (300 mL), dried over sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified over silica gel (400 g) eluting with heptanes to give compound (8) (50 g, 91% yield) as a light-yellow oil that slowly turned to an off-white solid on standing. extracted with ethyl acetate (3×400 mL) The combined organic layers were washed with saturated brine (300 mL) dried over sodium sulfate concentrated under reduced pressure The resulting residue was purified over silica gel (400 g) eluting with heptanes

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of compound 4 (40 g, 205 mmol, 1 equiv), (biphenyl-2-yl)boronic acid (81.2 g, 410 mmol, 2 equiv), powdered potassium carbonate (85 g, 615 mmol, 3 equiv), and bis(triphenylphosphine)palladium(II)dichloride (7.2 g, 10.3 mmol, 0.05 equiv), 1,4-dioxane (300 mL) and water (150 mL) was heated overnight at 80° C. The reaction was poured into 500 mL of water and extracted with ethyl acetate (3×400 mL). The combined organic layers were washed with saturated brine (300 mL), dried over sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified over silica gel (400 g) eluting with heptanes to give compound (8) (50 g, 91% yield) as a light-yellow oil that slowly turned to an off-white solid on standing. extracted with ethyl acetate (3×400 mL) The combined organic layers were washed with saturated brine (300 mL) dried over sodium sulfate concentrated under reduced pressure The resulting residue was purified over silica gel (400 g) eluting with heptanes

Conditions: temp:-67.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Under an atmosphere of argon, 2-bromobiphenyl (20 g, 86 mmole) was dissolved into anhydrous ether (200 ml) and the resultant solution was cooled at −35° C. in a dry ice/methanol bath. To the cooled solution, a hexane solution of n-butyllithium (1.50 mole/liter, 63 ml, 95 mmole) was added dropwise and the resultant mixture was stirred at −20° C. for 1 hour. After the reaction mixture was cooled at −67° C., a solution (50 ml) of triisopropoxyborane (50 ml, 0.22 mole, 2.5 eq) in anhydrous ether was added and the resultant mixture was stirred at −65° C. for 1 hour and at the room temperature for 2 hours and left standing for one night. To the obtained reaction mixture, a 10% hydrochloric acid (200 ml) was added. After the resultant mixture was stirred at the room temperature for 1 hour, the formed organic layer was separated, washed with a saturated aqueous solution of sodium chloride (50 ml) and dried with anhydrous magnesium sulfate. The solid obtained after removing the solvent by distillation was washed with hexane and a white solid (11 g, 62%) was obtained. left standing for one night To the obtained reaction mixture the formed organic layer was separated washed with a saturated aqueous solution of sodium chloride (50 ml) dried with anhydrous magnesium sulfate The solid obtained after removing the solvent by distillation was washed with hexane

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 14.7 g (31.5 mmol) of 2,8-dibromo-6,6,12,12-tetramethyl-6,12-dihydroindeno[1,2-b]fluorene, 6.5 g (33 mmol) of biphenyl-2-ylboronic acid, 0.36 g (0.3 mmol) of tetrakis(triphenylphosphine) palladium, 32 ml of 2M Na2CO3, 60 ml of EtOH and 150 ml toluene was degassed and placed under nitrogen, and then heated at 100° C. for 24 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The organic layer was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica (hexane-dichloromethane) to give product 9.7 g (17.9 mmol, 57%). 1H NMR (CDCl3, 400 MHz): chemical shift (ppm): 7.78 (d, J=8.0 Hz, 1H), 7.65˜7.61 (m, 1H), 7.56 (d, J=8.0 Hz, 1H), 7.51˜7.21 (m, 10H), 7.18 (s, 2H), 7.08˜6.99 (m, 2H), 1.83 (s, 6H), 1.81 (s, 6H) was degassed the reaction to cool to room temperature The organic layer was extracted with ethyl acetate and water dried with anhydrous magnesium sulfate the solvent was removed the residue was purified by column chromatography on silica (hexane-dichloromethane)

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 15.3 g (37 mmol) of 3,8-dibromo-11,12-dihydroindolo[2,3-a]carbazole, 18.3 g (92.4 mmol) of biphenyl-2-ylboronic acid, 0.86 g (0.8 mmol) of Pd(PPh3)4, 55 ml of 2M Na2CO3, 100 ml of EtOH and 200 ml toluene was degassed and placed under nitrogen, and then heated at 100° C. for 24 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The organic layer was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica to give product (12.2 g, 21.8 mmol, 59%). was degassed the reaction to cool to room temperature The organic layer was extracted with ethyl acetate and water dried with anhydrous magnesium sulfate the solvent was removed the residue was purified by column chromatography on silica

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 40.1 g (100 mmol) of 3,6-dibromo-9-phenyl-9H-carbazole, 21.8 g (110 mmol) of biphenyl-2-ylboronic acid, 2.31 g (2 mmol) of Pd(PPh3)4, 75 ml of 2M Na2CO3, 150 ml of EtOH and 300 ml toluene was degassed and placed under nitrogen, and then heated at 100° C. for 12 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The organic layer was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica to give product (19.9 g, 42.0 mmol, 42%) as a white solid. was degassed the reaction to cool to room temperature The organic layer was extracted with ethyl acetate and water dried with anhydrous magnesium sulfate the solvent was removed the residue was purified by column chromatography on silica

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 35.2 g (100 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene, 21.8 g (110 mmol) of biphenyl-2-ylboronic acid, 2.31 g (2 mmol) of Pd(PPh3)4, 75 ml of 2M Na2CO3, 150 ml of EtOH and 300 ml toluene was degassed and placed under nitrogen, and then heated at 100° C. for 12 h. After finishing the reaction, the mixture was allowed to cool to room temperature. The organic layer was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica to give product (26.8 g, 63.0 mmol, 63%) as a white solid. was degassed the reaction to cool to room temperature The organic layer was extracted with ethyl acetate and water dried with anhydrous magnesium sulfate the solvent was removed the residue was purified by column chromatography on silica

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 35.2 g (100 mmol) of 2,7-dibromo-9,9-dimethyl-9H-fluorene, 21.8 g (110 mmol) of biphenyl-2-ylboronic acid, 2.31 g (2 mmol) of Tetrakis(triphenylphosphine)palladium, 75 ml of 2M Na2CO3, 150 ml of EtOH and 300 ml toluene was degassed and placed under nitrogen, and then heated at 100° C. for 12 h. After finishing the reaction. The mixture was allowed to cool to room temperature. The organic layer was extracted with ethyl acetate and water, dried with anhydrous magnesium sulfate, the solvent was removed and the residue was purified by column chromatography on silica (hexane-dichloromethane) to give product (26.8 g, 63.0 mmol, 63%) as a white solid. 1H NMR (CDCl3, 400 MHz): δ 7.61 (d, J=7.8 Hz, 1H), 7.55˜7.53 (m, 2H), 7.49˜7.42 (m, 5H), 7.29 (d, J=8.0 Hz, 1H), 7.20˜7.14 (m, 5H), 6.98 (s, 1H), 1.21 (s, 6H) was degassed the reaction to cool to room temperature The organic layer was extracted with ethyl acetate and water dried with anhydrous magnesium sulfate the solvent was removed the residue was purified by column chromatography on silica (hexane-dichloromethane)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The procedure of Synthesis Example 1 was repeated except that 2-naphthalene boronic acid in place of phenylboronic acid was used, and then 7.5 g of 1-bromo-4-(naphthalene-2-yl)naphthalene of white crystal was obtained (yield: 43%). Synthesis Example 3 (Synthesis of 2-(biphenyl-2-yl)-6-bromonaphthelene) 15 g of 2,6-dibromonaphthalene on the market, 12.5 g of 2-biphenylboronic acid and 1.8 g of tetrakis(triphenylphophine)palladium were mixed, followed by argon displacement. After adding 250 ml of toluene and 90 ml of 2M sodium carbonate aqueous solution thereto, it was refluxed on heating for 7 hours. After standing to cool, the organic layer was extracted by toluene, and then it was washed by water and saturated salt water. Subsequently the organic layer was dried by using sodium sulfate anhydride, and then the solvent was removed by distillation. The product was refined through a silica gel chromatography and then 10.9 g of 2-(biphenyl-2-yl)-6-bromonaphthalene of white crystal was obtained (yield: 58%). were mixed it was refluxed on heating for 7 hours to cool the organic layer was extracted by toluene it was washed by water and saturated salt water Subsequently the organic layer was dried the solvent was removed by distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The procedure of Synthesis Example 1 was repeated except that 2-naphthalene boronic acid in place of phenylboronic acid was used, and then 7.5 g of 1-bromo-4-(naphthalene-2-yl)naphthalene of white crystal was obtained (yield: 43%). Synthesis Example 3 (Synthesis of 2-(biphenyl-2-yl)-6-bromonaphthelene) 15 g of 2,6-dibromonaphthalene on the market, 12.5 g of 2-biphenylboronic acid and 1.8 g of tetrakis(triphenylphophine)palladium were mixed, followed by argon displacement. After adding 250 ml of toluene and 90 ml of 2M sodium carbonate aqueous solution thereto, it was refluxed on heating for 7 hours. After standing to cool, the organic layer was extracted by toluene, and then it was washed by water and saturated salt water. Subsequently the organic layer was dried by using sodium sulfate anhydride, and then the solvent was removed by distillation. The product was refined through a silica gel chromatography and then 10.9 g of 2-(biphenyl-2-yl)-6-bromonaphthalene of white crystal was obtained (yield: 58%). were mixed it was refluxed on heating for 7 hours to cool the organic layer was extracted by toluene it was washed by water and saturated salt water Subsequently the organic layer was dried the solvent was removed by distillation