(3-(carbazole-9H)Phenyl)Pinacol ester

Under nitrogen flow, the target compound 11 (10.5 g), bis(pinacolate)diboron (9.93 g), potassium acetate (10.9 g), and anhydrous dimethylsulfoxide (190 ml) were stirred while heating to 60°C for 15 min, and [1, 1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex (0.799 g) was added thereto. The resulting mixture was stirred while heating to 80°C for 9 hr and then allowed to cool to room temperature. To the reaction solution, water (250 ml) and toluene (500 ml) were added, and the resulting mixture was stirred. After the water layer was reextracted twice with toluene, the organic layers were mixed. Further, magnesium sulfate and active clay were added thereto. The magnesium sulfate and active clay were removed by filtration, and the toluene was evaporated under reduced pressure. The precipitated crystal was washed with cold methanol and dried under reduced pressure to obtain a target compound 12 (9.86percent, yield: 80percent) as a white crystal.In 500 mL three-necked flask, followed by adding intermediate M7 (20g, 62.lmmol), bis (pinacolato) diboron (23.6g, 93.2mmol), CH3COOK (17.5g, 178.2mmol), 1, 4- dioxane, 300 mL, and S-phos (5.35g, 13.04mmol), N2 replaced three times, was added Pd2 (dba) 3 (3.98g, 4.35mmol) and heated to reflux. After 24h the reaction was stopped.It cooled to room temperature, filtered, and the filtrate was collected, concentrated, and purified by column chromatography (dichloromethane: n-hexane = 0-1 as the mobile phase), to receive an off-white solid 17.4g (76percent), A mixture of 1B (6.55 g, 20.4 mmol), bis(pinacolato)diboron (6.22 g, 24.5 mmol), [1, 1′-Bis(diphenylphosphino)ferrocene]dichloropalladium (747 mg, 1.02 mmol), and potassium acetate (5.88 g, 60 mmol) in dimethylformamide (DMF) (anhydrous, 50 mL) was degassed for 45 minutes. The mixture was further degassed by being heated to about 85° C. overnight under argon. After cooling to RT, the mixture was poured into DCM (250 mL) and solids were filtered off. The filtrate was washed with water (2×300 mL), dried over sodium sulfate, and loaded onto silica gel. Flash column (gradient of 10percent to 30percent DCM in hexanes) and precipitation from DCM/MeOH gave 5.17 g of 1C; 69percent yield, pure by HNMR.Step 1 in the manufacturing of the compound (3.0 g, 9.3 mmol), bis (pinacolato) di boron (2.6 g, 10 mmol), potassium acetate (2.7 g, 28 mmol) and [bis (diphenylphosphino)ferrocene] dichloropalladium (0) complex (0.32 g, 0.39 mmol) and then the presence of nitrogen, for 24 hours at 80 dissolved in dioxane (60 ml), and stirred. After the reaction was terminated, cooled to ambient temperature, the reaction mixture was filtered through celite. Pour water to the filtrate, extracted with ethyl acetate, and wash the organic layer extracted with brine. The washed organic layer was dried over magnesium sulfate and purified by column chromatography (silica gel), the desired compound (2.3 g, 68percent) was obtained.4 was prepared as follows: a mixture of compound 3 (see Kido, J.; Su, S. -J.; Sasabe, H.; and, Takeda, T., Chem. Mater. 2008, 20(5), 1691-1693, which is incorporated by reference herein for its relevant teachings) (5.45 g, 16.9 mmol), bis(pinacolato)diboron (9.020 g, 35.52 mmol), [1, 1'-bis(diphenylphosphino)-ferrocene]dichloropalladium(II) (0.743 g, 1.02 mmol), potassium acetate (4.980, 50.75 mmol) and anhydrous toluene (110 mL) was degassed with argon for 1 h. while stirring. 9- (3-chlorophenyl) -9H-carbazole 20 g (72 mmol), 4, 4, 4 ', 4', 5, 5, 5 ', 5'-octamethyl-2, 2'-bi (1, 3 , 2-dioxaborolane) 20.1 g (79.2 mmol).Pd (dppf) Cl2 2.9 g (3.6 mmol), KOAc 21.2g (216 mmol) was added and 500 mL dioxane was added to the reaction solution. The mixture was heated under reflux for 12 hours at 130°C . Then cooled to room temperature and stop the reaction with 300 mL aqueous ammonium chloride solution to the reaction solution. Extract the mixture with E.A 500 mL, and washed with distilled water. The resulting organic layer was dried over anhydrous MgSO4, was evaporated under reduced pressure, and purified by silica gel column chromatography to give the title compound 20.0 g (75percent yield).I-6 (145 g, 522 mmol) was dissolved in 1, 600 mL of dimethylforamide (DMF) in a nitrogen atmosphere, Bis (pinacolato) diboron (159 g, 626 mmol)And (1, 1-bis (diphenylphosphine) ferrocene) dichloropalladium (II) (4.26 g, 5.22 mmol)Potassium acetate (128 g, 1, 305 mmol) was added and the mixture was heated at 150 ° C for 50 hours to reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, And dried in a vacuum oven.The residue thus obtained was separated and purified by flash column chromatography to obtain Compound I-7 (127 g, 66percent).Under a nitrogen atmosphere, 129 g (0.4 mol) of the compound (E) was dissolved in 600 mL of THF and cooled to -60 ° C. 263 mL of normal butyllithium (1.6 M hexane solution) was added dropwise and the mixture was stirred for 1 hour. 81.87 g (0.44 mol) of 2-isopropoxy-4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolane was added dropwise and the mixture was further stirred for 1 hour. The temperature of the mixture was raised to room temperature, neutralized with dilute hydrochloric acid, extracted with ethyl acetate / water, and the organic layer was washed with water and saturated brine and dried over magnesium sulfate. After distilling off the solvent under reduced pressure, purification with silica gel column chromatography (hexane / ethyl acetate) gave 105.5 g (yield 72percent) of compound (F).

Molecular Weight:369.3
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:2
Exact Mass:369.1900092
Monoisotopic Mass:369.1900092
Topological Polar Surface Area:23.4
Heavy Atom Count:28
Complexity:541
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes