1-溴-3-(叔丁基二甲基硅氧基)苯

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 3-bromophenol (50 g, 289 mmol) in 340 mL DMF was added Et3N (35 g, 347 mmol) and tert-butyldimethylsilyl chloride (52 g, 347 mmol). The mixture was stirred for 0.5 h, and then diluted with Et2O (2 L). The organic phase was washed with 5% aqueous HCl and brine, and dried over MgSO4. Flash chromatography using hexane:EtOAc (95:5) gave 80.1 g (96%) of product. The organic phase was washed with 5% aqueous HCl and brine dried over MgSO4

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of 3-bromophenol (50 g, 289 mmol) in 340 mL DMF was added Et3N (35 g, 347 mmol) and tert-butyldimethylsilyl chloride (52 g, 347 mmol). The mixture was stirred for 0.5 h, and then diluted with Et2O (2 L). The organic phase was washed with 5% aqueous HCl and brine, and dried over MgSO4. Flash chromatography using hexane:EtOAc (95:5) gave 80.1 g (96%) of product. The organic phase was washed with 5% aqueous HCl and brine dried over MgSO4

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Magnesium (0.226 g, 8.58 mmol) was flame dried in a 50 mL RB flask equipped with addition funnel and magnetic stirrer under N2. When the flask had cooled, anhydrous THF (25 mL), a pinch of iodine, and a THF solution of Rieke magnesium (1 mL) were added, followed by a small portion of 3-bromophenoxy-tert-butyl(dimethyl)silane (2.24 g, 7.80 mmol) in THF (3 mL) with slight warming to initiate the reaction. The remainder of the bromide solution (10 mL) was added dropwise over 15 min. After 0.5 h this Grignard solution was added to a solution of glutaric anhydride (0.89 g, 7.8 mmol) in THF (10 mL) with cooling in an ice-H2O bath. After 2 h, the reaction mixture was diluted with EtOAc and washed with 1N NaOH (5×) to extract the product. The aqueous basic solution was cooled in an ice-H2O bath and acidified with 12N HCl, then extracted with CH2Cl2 (3×50 mL). The organic layers were combined, washed with brine, dried (MgSO4), filtered and concentrated to give the crude product. Purification on an ISCO Combiflash eluting with 3-7% MeOH/CH2Cl2 w/NH4OH gave the title compound. MS(M+1)323. dried in a 50 mL RB flask equipped with addition funnel and magnetic stirrer under N2 When the flask had cooled anhydrous THF (25 mL), a pinch of iodine, and a THF solution of Rieke magnesium (1 mL) were added with slight warming the reaction with cooling in an ice-H2O bath washed with 1N NaOH (5×) to extract the product The aqueous basic solution was cooled in an ice-H2O bath extracted with CH2Cl2 (3×50 mL) washed with brine dried (MgSO4) filtered concentrated to give the crude product Purification on an ISCO Combiflash eluting with 3-7% MeOH/CH2Cl2

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3-Bromophenol (7.65 g, 0.044 mol) was dissolved in anhydrous CH2Cl2 (50 mL) at room temperature and treated with imidazole (6.02 g, 0.088 mmol) and tert-butyl(dimethyl)silyl chloride (8.0 g, 0.053 mol). After stirring for 3 days, the reaction mixture was partitioned between CH2Cl2 and H2O. The aqueous layer was washed with CH2Cl2 (2×), the organics combined and dried (Na2SO4). Filtration and concentration in vacuo followed by trituration of the residue to remove the solid imidazole gave the title compound. the reaction mixture was partitioned between CH2Cl2 and H2O The aqueous layer was washed with CH2Cl2 (2×) dried (Na2SO4) Filtration and concentration in vacuo to remove the solid imidazole

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3-Bromophenol (7.65 g, 0.044 mol) was dissolved in anhydrous CH2Cl2 (50 mL) at room temperature and treated with imidazole (6.02 g, 0.088 mmol) and tert-butyl(dimethyl)silyl chloride (8.0 g, 0.053 mol). After stirring for 3 days, the reaction mixture was partitioned between CH2Cl2 and H2O. The aqueous layer was washed with CH2Cl2 (2×), the organics combined and dried (Na2SO4). Filtration and concentration in vacuo followed by trituration of the residue to remove the solid imidazole gave the title compound. the reaction mixture was partitioned between CH2Cl2 and H2O The aqueous layer was washed with CH2Cl2 (2×) dried (Na2SO4) Filtration and concentration in vacuo to remove the solid imidazole

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3-Bromophenoxy-tert-butyldimethylsilane (146 g, 0.51 mol, Example 1, infra) was dissolved in dry tetrahydrofuran under nitrogen and cooled to −78° C. A solution of 1.6 M n-butyllithium in hexane (318 mL, 0.51 mol) was added dropwise at a rate to maintain temperature below −70° C. The reaction was stirred for 30 minutes after the addition was complete, and the cold solution was transferred to another vessel containing a cold (−78° C.) solution of 4-bromobenzaldehyde (94.3 g, 0.51 mol) in 1000 mL of dry tetrahydrofuran under nitrogen. The transfer rate was monitored to maintain reaction temperature below −70° C. The reaction mixture was stirred for another 45 minutes at −78° C. and then quenched with 100 mL of saturated aqueous ammonium chloride. After warming to room temperature, the mixture was diluted with 2000 mL of diethyl ether and washed with 2000 mL of water followed by 500 mL of saturated sodium chloride. The ethereal solution was dried over sodium sulfate and the solvent removed to give 197.2 g of crude α-(4-bromophenyl)-3-(tert-butyldimethylsilyloxy)benzyl alcohol as a yellow oil. to maintain temperature below −70° C after the addition the cold solution was transferred to another vessel to maintain reaction temperature below −70° C The reaction mixture was stirred for another 45 minutes at −78° C. quenched with 100 mL of saturated aqueous ammonium chloride After warming to room temperature the mixture was diluted with 2000 mL of diethyl ether washed with 2000 mL of water The ethereal solution was dried over sodium sulfate the solvent removed