(4-bromo-2-methylsulfonylphenyl)methanol

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

Procedure: To a mixture of (4-bromo-2-methansulfonyl-phenyl)-methanol (0.73 g, 2.78 mmol), sodium hydride (0.030 g, 8.4 mmol), and THF (10 mL) was added iodomethane (0.21 mL, 3.36 mmol). After 1 h, the reaction was poured into water (40 mL), diluted in CH2Cl2, and washed with brine (40 mL). The organic layer was dried over (Na2SO4), filtered, concentrated and purified by silica gel column chromatography to give 600 mg of 4-bromo-2-methansulfonyl-1-methoxymethyl-benzene. washed with brine (40 mL) The organic layer was dried over (Na2SO4) filtered concentrated purified by silica gel column chromatography

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

Procedure: To a solution of 4-bromo-2-methansulfonyl-benzaldehyde (1.0 g, 3.88 mmol) in EtOH (11 mL)/THF (2.5 mL) was added NaBH4 (1.29 g, 34.2 mmol) in three portions. The reaction was carefully quenched with water and the product was extracted with EtOAc, dried (Na2SO4), and purified by silica gel chromatography to give 735 mg of (4-bromo-2-methansulfonyl-phenyl)-methanol. The reaction was carefully quenched with water the product was extracted with EtOAc dried (Na2SO4) purified by silica gel chromatography

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

Procedure: To a mixture of (4-bromo-2-methansulfonyl-phenyl)-methanol (0.73 g, 2.78 mmol), sodium hydride (0.030 g, 8.4 mmol), and THF (10 mL) was added iodomethane (0.21 mL, 3.36 mmol). After 1 h, the reaction was poured into water (40 mL), diluted in CH2Cl2, and washed with brine (40 mL). The organic layer was dried over (Na2SO4), filtered, concentrated and purified by silica gel column chromatography to give 600 mg of 4-bromo-2-methansulfonyl-1-methoxymethyl-benzene. washed with brine (40 mL) The organic layer was dried over (Na2SO4) filtered concentrated purified by silica gel column chromatography

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

Procedure: To a solution of 4-bromo-2-methansulfonyl-benzaldehyde (1.0 g, 3.88 mmol) in EtOH (11 mL)/THF (2.5 mL) was added NaBH4 (1.29 g, 34.2 mmol) in three portions. The reaction was carefully quenched with water and the product was extracted with EtOAc, dried (Na2SO4), and purified by silica gel chromatography to give 735 mg of (4-bromo-2-methansulfonyl-phenyl)-methanol. The reaction was carefully quenched with water the product was extracted with EtOAc dried (Na2SO4) purified by silica gel chromatography

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

Procedure: To a mixture of (4-bromo-2-methansulfonyl-phenyl)-methanol (0.73 g, 2.78 mmol), sodium hydride (0.030 g, 8.4 mmol), and THF (10 mL) was added iodomethane (0.21 mL, 3.36 mmol). After 1 h, the reaction was poured into water (40 mL), diluted in CH2Cl2, and washed with brine (40 mL). The organic layer was dried over (Na2SO4), filtered, concentrated and purified by silica gel column chromatography to give 600 mg of 4-bromo-2-methansulfonyl-1-methoxymethyl-benzene. washed with brine (40 mL) The organic layer was dried over (Na2SO4) filtered concentrated purified by silica gel column chromatography

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

Procedure: To a solution of 4-bromo-2-methansulfonyl-benzaldehyde (1.0 g, 3.88 mmol) in EtOH (11 mL)/THF (2.5 mL) was added NaBH4 (1.29 g, 34.2 mmol) in three portions. The reaction was carefully quenched with water and the product was extracted with EtOAc, dried (Na2SO4), and purified by silica gel chromatography to give 735 mg of (4-bromo-2-methansulfonyl-phenyl)-methanol. The reaction was carefully quenched with water the product was extracted with EtOAc dried (Na2SO4) purified by silica gel chromatography

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of (4-bromo-2-methanesulfonyl-phenyl)-methanol (preparation 112) (100 mg, 0.38 mmol) in POBr3 (542 mg, 1.89 mmol) was added PBr3 (511 mg, 1.89 mmol). After the addition, the reaction mixture was stirred at 130° C. overnight. TLC (petroleum ether:EtOAc 1:1) showed the reaction was complete. The reaction was cooled to room temperature and then poured into brine (10 mL) and extracted with EtOAc (10 mL×2). The combined organic layers were washed with brine (10 mL×2), dried over sodium sulfate and concentrated in vacuo to give crude 4-bromo-1-bromomethyl-2-methanesulfonyl-benzene (200 mg, 80%) as a white solid. After the addition The reaction was cooled to room temperature extracted with EtOAc (10 mL×2) The combined organic layers were washed with brine (10 mL×2) dried over sodium sulfate concentrated in vacuo

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

Procedure: To a solution of (4-bromo-2-methanesulfonyl-phenyl)-methanol (preparation 112) (500 mg, 1.89 mmol) in DMF (10 mL) was added NaH (226 mg, 5.66 mmol, 60% in oil) at room temperature. After stirring at room temperature for 30 minutes, to above mixture was added MeI (230 mg, 10 mmol) at room temperature. The resulting mixture was stirred at room temperature for 3 hrs. TLC (petroleum ether:EtOAc 1:1) showed the reaction was complete. Then the mixture was poured into H2O (10 mL) and extracted with EtOAc (50 mL×3), washed with brine (10 mL×3), dried over sodium sulfate, concentrated in vacuo to give the residue, which was purified by a Biotage silica gel cartridge (petroleum ether/EtOAc 1:1, Rf˜0.5) to give the title compound (200 mg, 40%) as yellow oil. The resulting mixture was stirred at room temperature for 3 hrs extracted with EtOAc (50 mL×3) washed with brine (10 mL×3) dried over sodium sulfate concentrated in vacuo to give the residue, which was purified by a Biotage silica gel cartridge (petroleum ether/EtOAc 1:1, Rf˜0.5)

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

Procedure: To a stirring solution of methyl 4-bromo-2-(methylsulfonyl)benzoate (1000 mg, 3.41 mmol) in THF (20 mL) at −78° C. was added DIBAL-H solution (1.0 M in hexanes, 7.50 ml, 2.20 equiv.) dropwise. The mixture was stirred for 15 min and then gradually warmed to room temperature and stirred for another 4 hour. LCMS indicated clean conversion of the starting material to the product. The reaction was quenched with sodium bicarbonate, and then concentrated to dryness. The resulting solids were stirred with DCM (100 ml) for 1 hour and then filtered. The solids were rinsed with EtOAc until the rinse was free of product. The combined filtrate were dried over sodium sulfate, concentrated to dryness to give the desired product (788 mg) stirred for another 4 hour The reaction was quenched with sodium bicarbonate concentrated to dryness The resulting solids were stirred with DCM (100 ml) for 1 hour filtered The solids were rinsed with EtOAc until the rinse The combined filtrate were dried over sodium sulfate concentrated to dryness