, Étude de l'influence de la taille de la chaîne
,
,
,
,
,
,
,
,
,
, After cooling to room temperature, a saturated aqueous solution of sodium hydrogen carbonate (30 mL) was added. The organic layer was extracted with dichloromethane and washed with brine. The combined organic extracts were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel, p.280
, :90) at 25 mL/min; collected fraction: 5-10 min], giving the title compound as a dark yellow powder (70.3 mg, 0.36 mmol); yield 43 %, pp.116-117
,
, Hz, 1H), 7.45 (td, J = 7.4, 1.2 Hz, 1H), 7.29 (td, J = 7.3, 1.2 Hz, 1H), vol.7, p.75
,
, 1-I-FO. 1-iodo-9H-fluoren-9-one Hydrochloric acid, vol.408, 1011.
, g, 5.12 mmol) in water (50 mL). The solution was cooled down to 0°C and was allowed to stir for 30 min. A solution of sodium nitrite (880 mg, 12.8 on silica gel [column conditions: silica cartridge (24 g)
, dichloromethane/light petroleum (30:70) at 30 mL/min
, CD 2 Cl 2 ) ? = 7.73 (dd, J = 8.0, 0.8 Hz, 1H), 7.66 (ddd, J = 7.4, 1.0 Hz, 1H), 7.61 -7.51 (m, 3H), 7.35 (ddd, J = 7.4, 6.7, 1.9 Hz, 1H), vol.7
, , vol.440, 1009.
, eq.) were dissolved in dry DMF (10 mL) under an argon atmosphere. The mixture was heated to 120°C and stirred for 15 min before a mixture of 1-iodo-9H-fluoren-9-one 1-I-FO (1.00 g, 3.27 mmol, 1.0 eq.), potassium fluoride (0.569 g, 9.80 mmol, 3.0 eq.) and phenylboronic acid (0.478 g, 3.92 mmol, 1.2 eq.) in dry DMF (15 mL) was added. The resulting mixture was stirred at 120°C overnight. After cooling to room temperature, water was added and the organic layer was extracted with dichloromethane and washed with brine. The combined organic extracts were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. After purification by flash chromatography on silica gel
, 35 mL/min; collected fraction: 5-15 min], a yellow powder was obtained (0.713 g, 2.78 mmol)
, CD 2 Cl 2 ) ? = 193, vol.37
, Absolute ethanol (20 mL) was added and the reaction mixture was concentrated under reduced pressure. The residue was dissolved in acetic acid (30 mL) and the solution was heated under reflux before concentrated hydrochloric acid (4 mL) was added. The resulting mixture was stirred under reflux overnight, then cooled down to room temperature and added to water at 0°C (100 mL). The organic phase was extracted with dichloromethane and washed with a saturated aqueous solution of sodium thiosulfate. The organic layer was then dried over magnesium sulfate, filtrated and concentrated. The residue was purified by flash chromatography on silica gel, vol.507, 1016.
, The product was recrystallized from cyclohexane to give a colourless powder (346 mg, 0.88 mmol), dichloromethane/light petroleum, vol.30
, CD 2 Cl 2 ) ? = 7.91 (dd, J = 7.6, 1.1 Hz, 1H), 7.90 (ddd, J = 7.6, 1.0 Hz, 1H), 7.45 (t, J = 7.6 Hz, 1H), 7.42 -7.38 (m, 2H), 7.38 -7.32 (m, 1H), 7.21 (td, J = 7.5, 1.1 Hz, 2H), 7.11 -7.02 (m, 1H)
, 20 (CH), 124.05 (2CH), 123.98 (CH), 120.65 (CH), 120.46 (2CH), 119.55 (CH), 66.39 (Cspiro), 127.81 (2CH), 127.78 (2CH), 126.98 (2CH), vol.126
, mL) was added dropwise to a stirring suspension of 2-amino-4-bromo benzophenone (2.00 g, 7.24 mmol) in water (10 mL). The resulting solution was heated to 60°C and stirred for 1 h. It was then cooled down to 0°C and sodium nitrite (1.00 g, 14.48 mmol) in water (5 mL) at 0°C was added dropwise. The resulting mixture was stirred overnight at room temperature and then heated to 50°C for 3 h. The yellow precipitate was filtered off and washed with water and cold absolute ethanol. The product was purified by flash chromatography on silica gel
, :80) at 35 mL/min, dichloromethane/light petroleum, vol.20, p.20
, CD 2 Cl 2 ) ? = 7.72 (dd, J = 1.5, 0.7 Hz, 1H), 7.65 (ddd, J = 7.3, 1.0, 1.0 Hz, 1H), 7.56 -7.45 (m, 4H), vol.7, p.46, 1009.
, After purification by flash chromatography on silica gel [column conditions: silica cartridge (24 g), potassium carbonate (960 mg, 6.94 mmol)
, 07 mmol); yield 89 %; mp 100-101°C; 1 H NMR (300 MHz, CD 2 Cl 2 ) ? = 7.77 (dd, J = 1.6, 0.7 Hz, 1H)
, 3-Ph-SBF. 3-phenyl-9,9'-spirobi[fluorene] 2-Iodo-1,1'-biphenyl (624 mg, 2.23 mmol, 1.15 eq.) was dissolved in dry THF (10 mL) and cooled down to -78°C. A 2.5 M pentane solution of n-BuLi (0.9 mL, 2.23 mmol, 1.15 eq.) was then added dropwise to the solution at -78°C. The resulting mixture was stirred at the same temperature for one hour and 3-phenyl-9H-fluoren-9-one 3-Ph-FO (500 mg, 1.94 mmol) dissolved in dry THF (5 mL) was added dropwise. The reaction mixture was allowed to warm up to room temperature and stirred overnight, vol.443, 1007.
, 74 mmol); yield 90 %; mp 100-105°C; 1 H NMR (300 MHz, CD 2 Cl 2 ) ? = 8.11 (dd, J = 1.8, 0.6 Hz, 1H), 7.96 (dt, J = 7.7, 1.0 Hz, 1H), 7.91 (dt, J = 7.6, 0.9 Hz, 2H), vol.1, p.42
, 41 (CH), 124.40 (2CH), vol.124, p.35
, The phenyl-fluorenone (65.4 mg, 0.25 mmol, 1 eq.) was dissolved in diethylene glycol (5 mL) and the solution was degassed with argon for 20 min while being heated to 100°C
, The aqueous phase was extracted with dichloromethane. The organic extracts were combined, washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel. 1-Ph-F. 1-phenyl-9H-fluorene The title compound was synthetized according to the ketone reduction procedure described above using 1-phenyl-9H-fluoren-9-one 1-Ph-FO. The residue was purified by flash chromatography on silica gel [column conditions: silica cartridge (4 g); solid deposit on Celite®; ? detection : (254 nm, 280 nm); light petroleum at 18 mL/min, Hydrazine monohydrate (0.06 mL, 1.27 mmol, 5 eq.) was added dropwise and the mixture was stirred overnight at 100°C. Potassium hydroxide (71.2 mg, 1.27 mmol, 5 eq.) in degassed water, p.7
, 10 (2CH), vol.129, p.7
, 2-Ph-F. 2-phenyl-9H-fluorene The title compound was synthetized according to the Suzuki general procedure using 2-bromo-9H-fluorene (200 mg, 0.81 mmol), phenylboronic acid (149 mg 1.22 mmol), potassium carbonate (338 mg, 2.45 mmol), Pd(dppf)Cl 2 .CH 2 Cl 2 (33.3 mg, 0.04 mmol) in DMF (10 mL). After purification by flash chromatography on silica gel, vol.426, p.30, 1059.
, CD 2 Cl 2 ) ? = 7.87 (dd, J = 7.9, 0.6 Hz, 1H), 7.85 -7.78 (m, 2H), 7.73 -7.67 (m, 2H), 7.65 (ddt, J = 7.9, 1.6, 0.7 Hz, 1H), 7.61 -7.55 (m, 1H), 7.53 -7.44 (m, 2H)
, 3-Ph-F. 3-phenyl-9H-fluorene The title compound was synthetized according to the ketone reduction procedure described above using 3-phenyl-9H-fluoren-9-one 3-Ph-FO. The residue was purified by flash chromatography on silica gel [column conditions: silica cartridge (4 g); solid deposit on Celite®; ? detection : (254 nm, 280 nm); light petroleum at 18 mL/min; collected fraction: 1-2 min] to give a colourless powder (36 mg, 0.15 mmol), = 410, vol.428, pp.129-165, 1018.
, HRMS calculated for C 19 H 15 : 243.1168
, 4-Ph-FO. 4-phenyl-9H-fluoren-9-one The title compound was synthetized according to the Suzuki general procedure using 4-bromo-9H-fluoren-9-one (100 mg, 0.38 mmol), phenylboronic acid (70.6 mg 0.58 mmol), potassium carbonate (157 mg, 1.14 mmol), Pd(dppf)Cl 2 .CH 2 Cl 2 (15.5 mg, 0.019 mmol) in DMF (5 mL). After purification by flash chromatography on silica gel, vol.407, 1008.
, 4-Ph-F. 4-phenyl-9H-fluorene The title compound was synthetized according to the ketone reduction procedure described above using 4-phenyl-9H-fluoren-9-one 4-Ph-FO. The residue was purified by flash chromatography on silica gel, CD 2 Cl 2 ) ? = 7.73 -7.58 (m, 2H), 7.59 -7.41 (m, 5H), 7.42 -7.29 (m, 2H), 7.28 -7.13 (m, 2H), 6.83 -6.72 (m, 1H). ; 13 C NMR (75 MHz, vol.432, 1000.
, 52 (CH), 123.35 compound as a yellow solid (1.33 g, 3.71 mmol); yield 78 %; mp ??°C; 1 H NMR (600 MHz, vol.124
, H, 3.99. 1,1''-BiSBF. 1,1''-bi, vol.9
, After 1 hour of stirring at -78°C, 1,1''biFO (1.79 g, 5.00 mmol, 1.00 eq.of concentrated HBr (2.43 g, 30.0 mmol, 20 eq.) was added to the mixture which was stirred at 110? for 5 h. The resulting mixture was cooled down to room temperature and poured into water (100 mL). The precipitate was isolated by filtration and purified by column chromatography on silica gel, ) was dissolved in 30 ml of THF under an argon atmosphere. The solution was cooled down to -78°C before a 2.4 M solution of nBuLi
, ) was dissolved in dry THF (30 mL) and cooled down to -78°C. A 2.5 M pentane solution of n-BuLi (2.62 mL, 6.56 mmol, 1.15 eq.) was then added dropwise to the solution at -78°C. The resulting mixture was stirred at the same temperature for one hour, vol.9, p.15
, Absolute ethanol (2 mL) was added and the reaction mixture was concentrated under reduced pressure. The residue was suspended in acetic acid (100 mL) and the solution was heated to 100°C until complete dissolution before concentrated hydrochloric acid (4 mL) was added dropwise. The resulting mixture was heated under reflux overnight. The reaction mixture was then cooled down to room temperature and a saturated solution of ammonium chloride (100 mL) was added. The organic material was extracted with dichloromethane (3 × 100 mL) and washed with a saturated aqueous solution of sodium thiosulfate (100 mL) and brine (2 × 100 mL). The organic layer was then dried over magnesium sulfate, filtrated and concentrated. The residue was purified by flash chromatography on silica gel, dissolved in dry THF (30 mL) was added dropwise. The reaction mixture was allowed to warm up to room temperature and stirred overnight
, 90) at 35 mL/min] to give a colourless powder (1.75 mg, 4.43 mmol), dichloromethane/light petroleum, vol.10
, Hz, 3H), 7.22 (dd, J = 8.1, 1.9 Hz, 1H), vol.6, p.60
, Diethyl ether (150 mL) was added. The organic layer was washed with water (2 × 100 mL) and brine (100 mL), dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel, mL/mmol) was added to the halogen derivative (1.0 eq.) under an argon atmosphere and the mixture was cooled down to -78°C. A 2.5 M solution of n-BuLi, vol.9, p.280
, 35 mL/min, a colourless powder was obtained (599 mg, 1.35 mmol); yield 67 %; 1 H NMR (300 MHz, CDCl 3 ) ? = 7.91 -7.78 (m, 5H)
, 2-dioxaborolane The title compound was synthetized according to the borylation general procedure using 3-Br-SBF (1.00 g, 2.53 mmol), n-BuLi (1.21 mL, 3.04 mmol) and tetramethyl-1,3,2-dioxaborolane (0.67 mL, 3.42 mmol). After purification by flash chromatography on silica gel, vol.9, p.280
, 35 mL/min; collected fraction], a colourless powder was obtained (0.833 g, 1.87 mmol)
,
, After purification by flash chromatography on silica gel [column conditions: silica cartridge (40 g)
, dichloromethane/light petroleum, vol.20, p.40
, a yellow powder was obtained (824 mg, 1.67 mmol)
, CDCl 3 ) ? = 7.90 (td, J = 7.5, 0.7 Hz, 2H)
, -yl)-9H-fluoren-9-one The title compound was synthetized according to the Suzuki general procedure using 1-Br-FO (345 mg, 1.33 mmol), 3-Bpin-SBF (707 mg 1.60 mmol), potassium carbonate (552 mg, 3.99 mmol), Pd(dppf)Cl 2 .CH 2 Cl 2 (54 mg, 0.07 mmol) in DMF (20 mL), (m, 7H), 7.25 (td, J = 7.2, 1.4 Hz, 1H), 7.13 (tdd, J = 7.5, 5.5, 1.1 Hz, 3H), 7.00 (dd, J = 7, vol.6
, dichloromethane/light petroleum, vol.20, p.35
, -yl)-9H-fluoren-9-one The title compound was synthetized according to the Suzuki general procedure using 1-Br-FO (380 mg, 1.47 mmol), 4-Bpin-SBF (759 mg 1.72 mmol), NMR (300 MHz, CDCl 3 ) ? = 8.02 (dd, J = 1.7, 0.7 Hz, 1H), 7.87 (d, J = 7.6, 0.9 Hz, 3H), 7.69 -7.46 (m, 5H), 7.44 -7.23 (m, 6H)
, dichloromethane/light petroleum, vol.20, p.35
, ) was dissolved in dry THF (8.8 mL/mmol) and cooled down to -78°C. A 2.5 M pentane solution of n-BuLi (1.5 eq.) was then added dropwise to the solution at -78°C. The resulting mixture was stirred at the same temperature for one hour and the corresponding 1-SBF fluorenone (1 eq.) dissolved in dry THF (12 mL/mmol) was added sodium thiosulfate (50 mL), water (2 × 50 mL) and brine (100 mL). The organic 1-Naph-FO. 1-(naphthalen-1-yl)-9H-fluoren-9-one The title compound was synthetized according to the Suzuki general procedure using 1-Br-FO (355 mg, 1.37 mmol), CDCl 3 ) ? = 7.87 (t, J = 6.9 Hz, 2H), 7.79 -7.68 (m, 1H), 7.66 (d, J = 7.4 Hz, 2H), 7.60 -7.49 (m, 2H), 7.46 -7.34 (m, 3H), 7.31 (dd, J = 7.4, 1.1 Hz, 1H), 7.25 -7.11 (m, 4H), 7.07 (d, J = 7.6 Hz, 1H), vol.7
, After purification by flash chromatography on silica gel [column conditions: silica cartridge (24 g); solid deposit on Celite®
, 80) at 35 mL/min], a yellow powder was obtained (300 mg, 0.98 mmol), dichloromethane/light petroleum, vol.20
, 62, 125.24, 124.30, 120.28, 119.69.; HRMS calculated for C 27 H 17 O: 357.12739, found: 357.1276 [M+H] + 1-Anth-FO. 1-(anthracen-9-yl)-9H-fluoren-9-one The title compound was synthetized according to the Suzuki general procedure using 1-Br-FO (355 mg, 1.37 mmol), 1-(anthracen-9-yl)-Bpin (500 mg 1.64 mmol), vol.7
, After purification by flash chromatography on silica gel [column conditions: silica cartridge (24 g); solid deposit on Celite®
, 78 mmol); yield 55 %; mp 236°C; 13 C N?R (75 ?Hz, solvent) ? = 192, vol.33
, Hz, 1H), 7.73 -7.57 (m, 3H), 7.56 -7.47 (m, 2H)
, After cooling to room temperature, a saturated solution of ammonium chloride was added. The organic layer was extracted with dichloromethane and washed with brine. The combined organic extracts were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel
, 80) at 35 mL/min] and then recrystallized from ethanol to give yellow needles (516 mg, 1.13 mmol), dichloromethane/light petroleum, vol.20
, 7.19 (dt, J = 8.1, 0.9 Hz, 2H).; HRMS calculated for C 25 H 15 NONa: 368.10458, found: 368.1043 [M+Na] + . 1-aryl-SBF general procedure 2-Iodo-1,1'-biphenyl (1.4 eq.) was dissolved in dry THF (8.8 mL/mmol) and cooled down to -78°C. A 2.5 M pentane solution of n-BuLi (1.5 eq.) was then added dropwise to the solution at -78°C. The resulting mixture was stirred at the same temperature for one hour and the corresponding 1-aryl fluorenone (1 eq.) dissolved in dry THF (12 mL/mmol) was added sodium thiosulfate (50 mL), water (2 × 50 mL) and brine (100 mL). The organic layer was then dried over magnesium sulfate, ? = 8.17 (dt, 2H), 7.74 -7.63 (m, 3H), 7.62 -7.49 (m, 2H), 7.50 -7.27 (m, 6H)
, The title compound was synthetized according to the 1-aryl-SBF general procedure using 2-Iodo-1,1'-biphenyl (320 mg 1.14 mmol) and 1-Naph-FO (250 mg 0.82 mmol). After purification by flash chromatography on silica gel
, XXX mmol); yield XX %; 1 H NMR (300 MHz, solvent) ? = 8.01 (dd, Hz, 1H), 7.96 (dd, J = 7.6, 1.0 Hz, 1H), 7.66 -7.46 (m, 3H), 7.50 -7.40 (m, 1H), vol.6
, The title compound was synthetized according to the 1-aryl-SBF general procedure using 2-Iodo-1,1'-biphenyl (220 mg 0.79 mmol) and 1-Anth-FO (200 mg 0.56 mmol). After purification by flash chromatography on silica gel
, 280 nm); light petroleum at 35 mL/min, a colourless powder was obtained (193 mg, 0.39 mmol)
, ? =8.15 -8.09 (m, 2H), 8.00 (dt, J = 7.7, 1.0 Hz, 1H), 7.79 -7.67 (m, 2H), 7.65 (t, J = 7.5 Hz, 1H), 7.40 (td, J = 7.5, 1.1 Hz, 1H), p.75
,
, The title compound was synthetized according to the 1-aryl-SBF general procedure using 2-Iodo-1,1'-biphenyl (275 mg 0.98 mmol) and 1-Phen-FO (250 mg 0.70 mmol). After purification by flash chromatography on silica gel
, 280 nm); light petroleum at 35 mL/min, a colourless powder was obtained (283 mg, 0.57 mmol)
, Hz, 1H), 6.58 -6.37 (m, 4H).; 13 C NMR (75 MHz, CD 2 Cl 2 ) ? = 150, Hz, 1H), 7.62 -7.53 (m, 2H), 7.49 -7.32 (m, 3H), 7.24 -6.95 (m, 9H), 6.87 -6.80 (m, 1H), 6.62 (dt, J = 7.6, 1.0
, The title compound was synthetized according to the 1-aryl-SBF general procedure using 2-Iodo-1,1'-biphenyl (424 mg 1.15 mmol) and 1-Pyre-FO (500 mg 1.31 mmol). After purification by flash chromatography on silica gel
, 280 nm); light petroleum at 35 mL/min, a colourless powder was obtained (417 mg, 0.80 mmol)
, ? = 8.13 (dd, J = 7.5, 1.3 Hz, 1H), 8.07 (dd, J = 7.7, 1.2 Hz, 1H), 8.05 -8.01 (m, 1H), 7.99 (dt, J = 7.7, 0.9 Hz, 2H), 7.98 (d, J = 6.6 Hz, 1H), 7.96 -7.87 (m, 2H)
, -yl)-9H-carbazole The title compound was synthetized according to the 1-aryl-SBF general procedure using 2-Iodo-1, mmol). After purification by flash chromatography on silica gel, vol.9, p.1
, 280 nm); light petroleum at 35 mL/min, a colourless powder was obtained (100 mg, 0.29 mmol)
, ? = 8.13 (dd, J = 7.6, 1.0 Hz, 1H), 7.99 (dt, J = 7.7, 1.0 Hz, 1H), 7.76 (ddd, J = 7.7, 1.3, 0.7 Hz, 2H), 7.65 (t, J = 7.7 Hz, 1H), 7.43 (td, J = 7.6, 1.1 Hz, 1H), 7.12 (td, J = 7.5, 1.1 Hz, 1H), 7.07 (dd, J = 7.8, 1.1 Hz, 1H), 6.98 -6.74 (m, 10H), 6.71 -6.61 (m, 2H), 6.51 (dt, J = 7.7, 1.0 Hz, 1H), vol.6
, , vol.4, p.7
, FdiEt-2BPin (250 mg, 0.530 mmol, 1 eq.), cesium fluoride (480 mg, 3.16 mmol, 6 eq
, ) were dissolved in 20 mL of anhydrous THF under an argon atmosphere. The solution was stirred under reflux for 24 h. The solvent was removed under reduced pressure and the resulting brown crude was further dried under vacuum at 75°C for 12 to 24 h. Triphenylphosphine (2074 mg, 7.91 mmol, 15 eq.) was added and anhydrous toluene (30 mL) was then added under an argon atmosphere. The solution was stirred at room temperature for 30 min and then stirred at 100°C for 24 h. The solvent was removed under reduced pressure and water (100 mL) was added. The organic materials were extracted with dichloromethane (3 ? 50 mL) and the resulting organic layer was washed with brine (3 ? 50 mL), dried over magnesium sulfate and concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel, vol.1, p.5
, :80) at 40 m?/min, dichloromethane/light petroleum, vol.20
, 280 nm); cyclohexane at 15 m?/min; first collected fraction] to give the title compound as a yellow solid (14 mg, 0.016 mmol); yield 12%; 1 H NMR (300 MHz, CD 2 Cl 2 ) ? = 7.60 (dd
, Hz, 4 ? 3H); 13 C NMR (75 MHz, CD 2 Cl 2 ) ? = 152.0 (4Cq ar ), vol.141
, M+
, , vol.409, p.347
, LP-diEt-F. 9,9-octaethyl-9H-2,7-quaterfluorene The title compound was obtained from the same procedure as [4]C-diEt-F through column
, Cq ar ), 141.1 (Cq ar ), 141.1 (Cq ar ), vol.151
, HRMS calculated for C, vol.68
, , vol.409, 1016.
, 9-dibutyl-9H-fluorene The title compound was synthesised according to a previously described procedure, vol.2, p.11
, DMSO (20 mL) were added triethylbenzylammonium chloride (425 mg, 1.87 mmol, 0.25 eq.) and tetrabutylammonium chloride (425 mg, 1.53 mmol, 0.20 eq.), then a 25 M aqueous solution of sodium hydroxide (10 mL, 247 mmol, 32 eq.), and finally bromobutane (4.67 mL, 43.21 mmol, 5.6 eq.). The reaction mixture was stirred at 100°C for 14 h. Water (150 mL) was added and the solution was extracted with diethyl ether (4 ? 50 mL). The organic layer was washed with water (2 ? 50 mL) and brine (50 mL), dried over sodium sulfate, filtrated and concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel, p.280
, nm
, 50 mL) was added to FdiBu-2Br (2.000 g, 4.58 mmol, 1.0 eq.) under an argon atmosphere and the mixture was cooled down to -78°C, p.50
, -dioxaborolane (4.50 mL, 22.0 mmol, 4.8 eq.) was added and the solution was stirred for 15 min. The mixture was allowed to warm up slowly to room temperature and stirred overnight. Water (150 mL) was added. The organic layer was extracted with diethyl ether, washed with water (3 ? 90 mL) and brine (90 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel, mL, 13.7 mmol, 3.0 eq.) was added dropwise and the solution was stirred at -78°C for 1 h. 2-isopropoxy-4,4, vol.5, p.20
, Yield 62%; 1 H NMR (300 MHz, CDCl 3 ) ? = 7.81 (d, J = 7.5 Hz, 2H), 7.75 (s, 2H), 7.72 (d, J = 7.6 Hz, 2H)
, , vol.4, p.7
, FdiBu-2BPin (265 mg, 0.50 mmol, 1 eq.), cesium fluoride (455 mg, 3.00 mmol, 6 eq
, 1 eq.) were dissolved in 20 mL of anhydrous THF under an argon atmosphere. The solution was stirred under reflux for 24 h. The solvent was removed under reduced pressure and the resulting brown crude was further dried under vacuum at 75°C for 12 to 24 h. Triphenylphosphine (1966 mg, 7.49 mmol, 329 15 eq.) was added and anhydrous 1,2-dichlorobenzene (30 mL) was then added under an argon atmosphere. The solution was stirred at room temperature for 30 min and then stirred at 180°C yellow solid (23 mg, 0.02 mmol), vol.1, p.5
, CD 2 Cl 2 ) ? = 154, 4CH), 124.17 (4CH), 122.64 (4CH, vol.140
, 7-fluorene The title compound was obtained from the same procedure as [4]CP-diBu-F from the size exclusion chromatography, vol.5
, CDCl 3 ) ? =7.65 (d, 1H), 7.62 (d, J = 8.1 Hz, 1H), mmol, vol.7, issue.11
, CD 2 Cl 2 ) ? = 152, vol.89, p.49
, Yield 88%; 1 H NMR (300 MHz
, , vol.5, p.7
, FdiHex-2BPin (295 mg, 0.50 mmol, 1 eq.), cesium fluoride (458 mg, 3.02 mmol, p.6
, 50 mmol, 1 eq.) were dissolved in 20 mL of anhydrous THF under an argon atmosphere. The solution was stirred under reflux for 24 h. The solvent was removed under reduced pressure and the resulting brown crude was further dried under vacuum at 75°C for 12 to 24 h. Triphenylphosphine (1979 mg, 7.55 mmol, 15 eq.) was added and anhydrous 1,2-dichlorobenzene (30 mL) was then added under an argon atmosphere. The solution was stirred at room temperature for 30 min and then stirred at 180°C, vol.1, p.5
, 0087 mmol)
, 30 (5CH), 124.59 (5CH), vol.126
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