N-(4-bromo-3-chlorophenyl)acetamide

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of potassium vinyltrifluoroborate (2.00 mmol), PdCl2 (0.04 mmol), PPh3 (0.12 mmol), Cs2CO3 (6.00 mmol), and N-(4-bromo-3-chlorophenyl)acetamide (2.00 mmol) in THF/H2O (9:1) (4 mL) was heated at 85° C. under an N2 atmosphere in a sealed tube. The reaction mixture was stirred at 85° C. for 22 h, then cooled to room temperature and diluted with H2O (3 mL) followed by extraction with CH2Cl2 (10 mL*3). The solvent was removed in vacuo, and the crude product was purified by silica gel chromatography (eluting with mixture of Hexanes and Ethyl acetate) to yield the vinylic arene. A solution of vinyl arene (2 mmol) in dry THF (10 mL) was treated with BH3-Me2S (1.6 mmol, 0.8 equiv) at 0° C. and the reaction mixture was warmed at room temperature and stirred for overnight, after which time 10 mL water was added to dilute the solution. Then 3M NaOH solution (0.93 mL) and 30% (w/w) hydrogen peroxide solution (1.54 mL) was added sequentially to the reaction at 0° C. The mixture was allowed to stir overnight at room temperature and was extracted with CH2Cl2 (20×3 mL). The organic layer was dried with MgSO4 and concentrated in vacuum. Column chromatography was run using mixture of hexanes and ethyl acetate to afford corresponding alcohols. cooled to room temperature followed by extraction with CH2Cl2 (10 mL*3) The solvent was removed in vacuo the crude product was purified by silica gel chromatography (eluting with mixture of Hexanes and Ethyl acetate)

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

Procedure: To a solution of 4-bromo-3-chloroacetanilide (10.0 g, 40.2 mmol) in 50 mL THF is added 60% sodium hydride in mineral oil (2.40 g, 60.0 mmol) and the reaction mixture is stirred for 1 h at RT. The reaction mixture is cooled to 0° C., methyliodide (2.49 mL, 40.0 mmol) is added. After 2 h additional methyl iodide (0.25 mL, 4.0 mmol) is added and the reaction mixture is stirred at RT for 10 min. The reaction mixture is quenched with saturated aqueous ammonium chloride, filtered and extracted with diethyl ether. The organic phases are washed with brine, dried over Na2SO4 and evaporated to dryness. Yield: 10.3 g. The reaction mixture is cooled to 0° C. the reaction mixture is stirred at RT for 10 min The reaction mixture is quenched with saturated aqueous ammonium chloride filtered extracted with diethyl ether The organic phases are washed with brine dried over Na2SO4 evaporated to dryness

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of potassium vinyltrifluoroborate (2.00 mmol), PdCl2 (0.04 mmol), PPh3 (0.12 mmol), Cs2CO3 (6.00 mmol), and N-(4-bromo-3-chlorophenyl)acetamide (2.00 mmol) in THF/H2O (9:1) (4 mL) was heated at 85° C. under an N2 atmosphere in a sealed tube. The reaction mixture was stirred at 85° C. for 22 h, then cooled to room temperature and diluted with H2O (3 mL) followed by extraction with CH2Cl2 (10 mL*3). The solvent was removed in vacuo, and the crude product was purified by silica gel chromatography (eluting with mixture of Hexanes and Ethyl acetate) to yield the vinylic arene. A solution of vinyl arene (2 mmol) in dry THF (10 mL) was treated with BH3-Me2S (1.6 mmol, 0.8 equiv) at 0° C. and the reaction mixture was warmed at room temperature and stirred for overnight, after which time 10 mL water was added to dilute the solution. Then 3M NaOH solution (0.93 mL) and 30% (w/w) hydrogen peroxide solution (1.54 mL) was added sequentially to the reaction at 0° C. The mixture was allowed to stir overnight at room temperature and was extracted with CH2Cl2 (20×3 mL). The organic layer was dried with MgSO4 and concentrated in vacuum. Column chromatography was run using mixture of hexanes and ethyl acetate to afford corresponding alcohols. cooled to room temperature followed by extraction with CH2Cl2 (10 mL*3) The solvent was removed in vacuo the crude product was purified by silica gel chromatography (eluting with mixture of Hexanes and Ethyl acetate)