1-bromo-4-(methylsulfonylmethyl)benzene

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-bromo-4-((methylsulfonyl)methyl)benzene (1.5 g, 6.02 mmol), 1,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (4.97 g, 15.05 mmol), and silver carbonate (1.826 g, 6.62 mmol) were dissolved in THF (60.2 ml) and sparged with N2 for 15 min. Then Pd(PPh3)4 (0.348 g, 0.301 mmol) was added and the reaction was heated to 80° C. overnight. The reaction was then cooled to rt, filtered through Celite™ and concentrated in vacuo. The resulting residue was purified by column chromatography on a Biotage™ 50 g column by eluting with 5% to 50% EtOAc:Hex to yield the desired product. 1H NMR δ (ppm) 7.83 (d, 2H), 7.69 (d, 2H), 7.64 (d, 2H), 7.54 (d, 2H), 4.46 (s, 2H), 2.89 (s, 3H), 1.4 (12H). sparged with N2 for 15 min The reaction was then cooled to rt filtered through Celite™ concentrated in vacuo The resulting residue was purified by column chromatography on a Biotage™ 50 g column by eluting with 5% to 50% EtOAc

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 250 mL round-bottomed flask was charged with 4-bromobenzyl bromide (5 g, 20 mmol) and N,N-dimethylformamide (10.81 mL). Sodium methanesulfinate (3.06 g, 30 mmol) was added. The reaction mixture was stirred at 65° C. for 1 hour. The reaction mixture was cooled to ambient temperature and diluted with water. The resulting suspension was stirred for 10 minutes and filtered. The solid was rinsed with water and dried under house vacuum over the weekend to provide 4.75 g (95%) of the title compound. The reaction mixture was cooled to ambient temperature The resulting suspension was stirred for 10 minutes filtered The solid was rinsed with water dried under house vacuum over the weekend

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 250 mL round-bottomed flask was charged with 4-bromobenzyl bromide (5 g, 20 mmol) and N,N-dimethylformamide (10.81 mL). Sodium methanesulfinate (3.06 g, 30 mmol) was added. The reaction mixture was stirred at 65° C. for 1 hour. The reaction mixture was cooled to ambient temperature and diluted with water. The resulting suspension was stirred for 10 minutes and filtered. The solid was rinsed with water and dried under house vacuum over the weekend to provide 4.75 g (95%) of the title compound. The reaction mixture was cooled to ambient temperature The resulting suspension was stirred for 10 minutes filtered The solid was rinsed with water dried under house vacuum over the weekend

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 250 mL round-bottomed flask was charged with 4-bromobenzyl bromide (5 g, 20 mmol) and N,N-dimethylformamide (10.81 mL). Sodium methanesulfinate (3.06 g, 30 mmol) was added. The reaction mixture was stirred at 65° C. for 1 hour. The reaction mixture was cooled to ambient temperature and diluted with water. The resulting suspension was stirred for 10 minutes and filtered. The solid was rinsed with water and dried under vacuum to provide the title compound (4.75 g, 95% yield). The reaction mixture was cooled to ambient temperature The resulting suspension was stirred for 10 minutes filtered The solid was rinsed with water dried under vacuum

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

Procedure: p-Bromobenzyl bromide (500 mg, 2 mmol) was refluxed with MeSO2Na (306 mg, 3 mmol) in Ethanol for 1 hour. The reaction was cooled, concentrated and purified by flash column (50% acetone/hexanes) to give the desired product. The reaction was cooled concentrated purified by flash column (50% acetone/hexanes)

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

Procedure: p-Bromobenzyl bromide (500 mg, 2 mmol) was refluxed with MeSO2Na (306 mg, 3 mmol) in Ethanol for 1 hour. The reaction was cooled, concentrated and purified by flash column (50% acetone/hexanes) to give the desired product. The reaction was cooled concentrated purified by flash column (50% acetone/hexanes)

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 250 mL round-bottomed flask was charged with 4-bromobenzyl bromide (5 g, 20 mmol) and N,N-dimethylformamide (10.81 mL). Sodium methanesulfinate (3.06 g, 30 mmol) was added. The reaction mixture was stirred at 65° C. for 1 hour. The reaction mixture was cooled to ambient temperature and diluted with water. The resulting suspension was stirred for 10 minutes and filtered. The solid was rinsed with water and dried under house vacuum over the weekend to provide 4.75 g (95%) of the title compound. The reaction mixture was cooled to ambient temperature The resulting suspension was stirred for 10 minutes filtered The solid was rinsed with water dried under house vacuum over the weekend

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

Procedure: Boronic acid 4 (200 mg, 0.51 mmol) is coupled to aryl bromide 197 (127 mg, 0.51 mmol) using Method A. On filtration of the cooled reaction mixture through celite and removal of the solvents in vacuo, the crude residue obtained is used in the next synthetic step without further purification. On filtration of the cooled reaction mixture through celite and removal of the solvents in vacuo

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A stirred suspension of 4-bromobenzyl bromide (1.0 g, 4.0 mmol) and sodium methanesulfinate (2.04 g, 20 mmol) in DMF (10 mL) is heated 1 h at 60° C. The reaction mixture is then cooled to RT, diluted with water (200 mL) and extracted into EtOAc (3×25 mL). The combined EtOAc phases are washed with water (2×50 mL) and brine (25 mL) then dried (MgSO4) and reduced in vacuo to afford the title compound. The reaction mixture is then cooled to RT extracted into EtOAc (3×25 mL) The combined EtOAc phases are washed with water (2×50 mL) and brine (25 mL) then dried (MgSO4)

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

Procedure: p-Bromobenzyl bromide (500 mg, 2 mmol) was refluxed with MeSO2Na (306 mg, 3 mmol) in Ethanol for 1 hour. The reaction was cooled, concentrated and purified by flash column (50% acetone/hexanes) to give the desired product. The reaction was cooled concentrated purified by flash column (50% acetone/hexanes)

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-bromo-4-((methylsulfonyl)methyl)benzene (1.5 g, 6.02 mmol), 1,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (4.97 g, 15.05 mmol), and silver carbonate (1.826 g, 6.62 mmol) were dissolved in THF (60.2 ml) and sparged with N2 for 15 min. Then Pd(PPh3)4 (0.348 g, 0.301 mmol) was added and the reaction was heated to 80° C. overnight. The reaction was then cooled to rt, filtered through Celite™ and concentrated in vacuo. The resulting residue was purified by column chromatography on a Biotage™ 50 g column by eluting with 5% to 50% EtOAc:Hex to yield the desired product. 1H NMR δ (ppm) 7.83 (d, 2H), 7.69 (d, 2H), 7.64 (d, 2H), 7.54 (d, 2H), 4.46 (s, 2H), 2.89 (s, 3H), 1.4 (12H). sparged with N2 for 15 min The reaction was then cooled to rt filtered through Celite™ concentrated in vacuo The resulting residue was purified by column chromatography on a Biotage™ 50 g column by eluting with 5% to 50% EtOAc

Conditions: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A 250 mL round-bottomed flask was charged with 4-bromobenzyl bromide (5 g, 20 mmol) and N,N-dimethylformamide (10.81 mL). Sodium methanesulfinate (3.06 g, 30 mmol) was added. The reaction mixture was stirred at 65° C. for 1 hour. The reaction mixture was cooled to ambient temperature and diluted with water. The resulting suspension was stirred for 10 minutes and filtered. The solid was rinsed with water and dried under vacuum to provide the title compound (4.75 g, 95% yield). The reaction mixture was cooled to ambient temperature The resulting suspension was stirred for 10 minutes filtered The solid was rinsed with water dried under vacuum