9-Phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole

General procedure: A solution of haloarene (1.0 mmol ratio), bis(pinacolate)diboron (1.2 mmol ratio), KOAc (1.5 mmol ratio), andPdCl2(dppf) (0.02 mmol ratio) in dry 1, 4-dioxane (20 ml)was refluxed for overnight under N2. After being cooledto room temperature, the mixture was poured into H2Oand then extracted with dichloromethane. The combinedorganic layer was washed with brine and dried over magnesiumsulfate. The solvent was removed in vacuo andcrude product was purified by chromatography (SiO2) elutingwith a mixture of DCM and n-hexane to afford the pureproducts. 2.2.2.4. 9-Phenyl-3-(4, 4, 5, 5, -tetramethyl-1, 3, 2-dioxaborolan-2-yl)-9H-carbazole (3); 3-Bromo-9-phenyl-9H-carbazole (4 g, 12.4 mmol), bis(pinacolate)diboron (3.79 g, 14.9 mmol), KOAc (1.9 g, 18.6 mmol), and PdCl2(dppf) (0.14 g, 0.02 mmol) wereused to yield compound 3 (4.1 g, 88.4percent) as a white solid:m.p. = 160 °CSaid Sub 1-III-1 obtained in the synthesis (104.03g, 322.9mmol) senses a rotation velocity of the disk to a DMF to in round bottom flask , Bis (pinacolato) diboron (90.19g, 355.2mmol), Pd (dppf) Cl A stream of nitrogen 3-bromo-9-phenyl-9H-carbazole (174.0 g, 540.0 mmol), 4, 4, 4', 4', 5, 5, 5', 5'-octamethyl-2, 2'-bi(1, 3, 2-dioxaborolane) (150.8 g, 594.0 mmol), Pd(dppf)Cl2 (62.4 g, 54.0 mmol), KOAc (152.5 g, Mixing 1.62 mol ) and 1, 4-Dioxane (2800 ml) and stirred for 12 hours at 130°C. After reaction being terminated then ethyl acetate extraction of MgSO3-bromo-9-phenyl-9H-carbazole 50g (155.18mmol) and Pd (dppf) Cl2 3.41g (4.65mmol), bis (pinacolato) diboron (Bis (pinacolato) diboron) 51.32g (201.8 mmol) of potassium acetate and 45.8g (465.5mmol) was dissolved in 1, 4-dioxane (dioxane) 520ml was reflux and stirred for 12 hours under a nitrogen atmosphere and the reaction was extracted three times with dichloro methane and distilled water. The extract was dried with magnesium sulfite, filtered and the filtrate was concentrated under reduced pressure. The product n- hexane / dichloromethane (7: 3 by volume) to give a 43g silica gel column (yield: 75percent) of intermediate M-12 chromatography to yield the desired compound as a white solid.50 g (155.18 mmol) of 3-bromo-9-phenyl-9H-carbazole, 3.41 g (4.65 mmol) of Pd(dppf)Cl2, 51.32 g (201.8 mmol) of bis(pinacolato)diboron, and 45.8 g (465.5 mmol) of potassium acetate were dissolved in 520 ml of 1, 4-dioxane. The reactant was reflux-agitated under a nitrogen atmosphere for 12 hours and then three times extracted with dichloromethane and distilled water. The extracted solution was dried with magnesium sulfite and filtered, and the filtered solution was concentrated under a reduced pressure. The concentrated product was purified with n-hexane/dichloromethane (7:3 of a volume ratio) through silica gel column chromatography, obtaining 43 g of a white solid compound, an intermediate M-12 (75percent of a yield).3-bromo-9-phenyl-9H-carbazole (45.1 g, 140 mmol) to DMF 980mL dissolved after, Bispinacolborate (39.1 g, 154 mmol), PdCl2 (dppf) catalyst (3.43 g, 4.2 mmol), KOAc(41.3 g, was added as a 420 mmol) procedure after 24 hours with stirring to synthesize a borate compound, and then the resulting compound was separated over a silicagel column and recrystallization to give the borate compound 35.2 g (68percent).3-bromo-9-phenyl-9H-carbazole (45.1g, 140mmol) was dissolved in 980mL DMF, Bispinacolborate (39.1g, 154mmol), PdCl2 (dppf) catalyst (3.43g, 4.2mmol), KOAc (41.3g, 420mmol ) after the procedure to synthesize a borate compound as stirred for 24 hours after the addition, then the resulting compound was separated over a silicagel column and recrystallized borate compound 35.2g (yield 68percent was obtained).3-bromo-9-phenyl-9H-carbazole (45.1 g, 140mmol) was dissolved in 980 mL DMF, bis(pinacolato)diboron (39.1g, 154 mmol), PdCl2(dppf) catalyst (3.43g, 4.2 mmol) and KOAc (41.3g, 420 mmol) were added and stirred for 24 hours in order to synthesize a borate compound. The resulting compound was separated using silica gel column and recrystallized to obtain 35.2 g (68percent) of a borate compound.Sub-1 (45.1 g, 140 mmol) obtained by the above-mentioned synthesis was dissolved in 980 mL of DMF, and then double tanolate borate (39.1 g, 154 mmol), PdCl2 (dppf) (3.3 g, 4.2 mmol) and KOAc (41.3 g, 420 mmol) were added and stirred for 24 hours to synthesize a borate compound. With siliconeThe column was purified and the resulting compound was recrystallized to afford 35.2 g of the borate compound (68percent).3-bromo-9-phenyl-9H-carbazole (45.1 g, 140 mmol)after dissolving in 980 mL of DMF, bispinacolborate (39.1 g, 154mmol), PdCl2 (dppf) catalyst (3.43 g, 4.2 mmol) and KOAc (41.3 g, 420 mmol) were added in this order and stirred for 24 hours to synthesize a borate compound. The resulting compound was separated by silicagel column and recrystallization 35.2 g (68percent) of a borate compound was obtained.3-bromo-9-phenyl-9H-carbazole (45.1 g, 140 mmol) was dissolved in 980 mL of DMF, bispinacolborate (39.1 g, 154 mmol), a PdClThe Sub 1-III-1 (33.69 g, 104.6 mmol) toa round bottom flask was charged with DMF (520ml) to dissolve later, bis(pinacolato)diboron (29.21 g, 115.0 mmol), Pd(dppf)Cl2 (2.56 g, 3.1 mmol), was added KOAc (30.79 g, 313.7mmol) and stirred at 90 . When the reaction iscomplete, the DMF was removed by distillation and extracted with water andCH2Cl2. The resulting compound and the organic layer was dried over MgSO4 andconcentrated to silicagel column and the product was recrystallized from 25.48 g(yield: 66percent) was obtained.Synthesis of Compound 10 Synthesis of 9-phenyl-3-(4, 4, 5, 5-tetramethyl-l, 3, 2-dioxaborolan-2-yl)-9H- carbazole. To a solution of 3-bromo-9-phenyl-9H-carbazole (20.3 g, 63 mmol) in THF (150 mL) at -78 °C was added 47.25 mL (75.8 mmol) of n-butyllithium (1.6 M in hexane). The mixture was stirred at -78 °C for 1 h. 21 mL (100 mmol) of 2-isopropoxy-4, 4, 5, 5-tetramethyl- [l, 3, 2]-dioxaborolane was added to the solution, and the resulting mixture was warmed to room temperature and stirred for 8 h. The mixture was poured into water and extracted with dichloromethane. The organic extracts were washed with brine and dried over magnesium sulfate. The solvent was removed by rotary evaporation, and recrystallization was made in hexane to afford 19.3 g (83 percent) of product as a white solid.3-bromo-9-phenyl-9H-carbazole (5 g, 15 mmol) was dissolved in 75 mL of anhydrous THFsolution and cooled to ?78 °C. Next, 10 mL of 2M n-butyllithium(16.5 mmol) was slowly added dropwise. After the mixture was stirredat ?78 °C for 30 min, 2.2 mL of 2-Isopropoxy-4, 4, 5, 5-tetramethyl-1, 3, 2-dioxa-borolane (19 mmol) was slowly added. The resulting mixturewas stirred for 3 h and gradually allowed warm to room temperature.After the reaction was completed, the crude product was extractedusing ethyl acetate and D.I water. Water remaining in theorganic layer is removed using anhydrous magnesium sulfate. Thesolvent was vaporized and recrystallized using hexane. (3.65 g, Yield68percent) 1H NMR (300 MHz, CDCl3): δ(ppm) 8.64 (s, 1H), 8.19–8.16 (d, 1H), 7.87–7.84 (d, 1H), 7.63–7.54 (m, 4H), 7.54–7.49 (t, 1H), 7.40–7.35 (m, 3H), 7.31–7.28 (d, 1H), 1.40 (s, 12H).After a mixed solution of 10 g (31.0 mmol) of 3-bromo-9-phenyl-9H-carbazole with anhydrous tetrahydrofuran (THF) was cooled down to ?78° C., about 3 equivalents of n-butyllithium (n-BuLi) was slowly dropwise added thereto and stirred at ?78° C. for about 2 hours. Then, about 3 equivalents of 2-isopropoxy-4, 4, 5, 5-tetramethyl-[1, 3, 2]-dioxaborolane was dropwise added to the solution and stirred at room temperature overnight. A resulting product was extracted with an organic solvent, followed by removing water with magnesium sulfate (MgSO100 mL of toluene was added to a mixture including 11.1 g (30.0 mmol) of compound 4, 9.1 g (36.0 mmol) of bis(pinacolato)diboron, 1.2 g (0.05 mole percent) of Pd(dppf)ClA 1000 mL 2-neck round bottom flask was charged with 3-iodo-9-phenyl-9H-carbazole (100.0 mmol, 36.9 g), bis(pinacolato)diboron(150.0 mmol, 38.1 g), PdCl2 (dppf) (3.0 mmol, 2.45 g), Potassium acetate (300.0 mmol, 29.4 g) was added, and nitrogenRespectively. 500 ml of dimethylformamide was added as a solvent, and the mixture was stirred at 80 ° C for 3 hours. The temperature of the reaction solution was lowered to room temperature and extracted with dichloromethane. The obtained extract was dried over MgSO4 and dried under reduced pressure to obtain crude product. The crude product was separated and purified by silica gel column chromatography to obtain 22.9 g (yield: 62percent) of intermediate 47-1 as a yellow solid.In a 1000 mL two-neck round bottom flask3-iodo-9-phenyl-9H-carbazole (100.0 mmol, 36.9 g)bis(pinacolato)diboron(150.0 mmol, 38.1 g), PdCl2 (dppf) (3.0 mmol, 2.45 g), Potassium acetate (300.0 mmol, 29.4 g) was charged and charged with nitrogen. 500 ml of dimethylformamide was added as a solvent, and the mixture was stirred at 80 ° C for 3 hours.The temperature of the reaction solution was lowered to room temperature and extracted with dichloromethane. The obtained extract was dried over MgSO4 and dried under reduced pressure to obtain crude product. The crude product was separated and purified by silica gel column chromatography to obtain 22.9 g (yield: 62percent) of intermediate 47-1 as a yellow solid.