1-bromo-3-methylsulfanylbenzene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:55.01; pressure:0.00; stir:

Procedure: dtbpy: A mixture of ortho- and meta-borylated products (118 mg, 72% yield, ortho/meta + para = 0.13); meta-Isomer 5o was obtained by further purification of the crude mixture by GPC (86 mg, 52% yield), yellow oil;

Conditions: temp:55.01; pressure:0.00; stir:

Procedure: Ligand 3f: A mixture of ortho- and meta-borylated products (130 mg, 79% yield, ortho/meta + para = 6.7); ortho-borylated product 4o was obtained by further purification by GPC (96 mg, 59% yield), colorless oil;

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: 3-Bromothioanisole was dissolved in methanol (20 ml) and cooled to 0° C. (ice/water bath). A solution of Oxone® (9.22 g) in water (30 ml) was added to this and the resultant cloudy slurry was stirred at room temperature for 3 hours. The reaction mixture was diluted with water and product extracted with dichloromethane. The combined fractions of dichloromethane were washed with brine and dried over anhydrous magnesium sulfate. After filtration, solvent was removed by evaporation under reduced pressure to give the sub-title compound as a solid (1.02 g). extracted with dichloromethane The combined fractions of dichloromethane were washed with brine dried over anhydrous magnesium sulfate After filtration, solvent was removed by evaporation under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: To a solution of 3-bromothiophenol (10 g) in acetone (250 mL) was added potassium carbonate (14.6 g) and iodomethane (4.28 mL). The heterogenous mixture was refluxed for 4 hrs., cooled to room temperature, filtered, and concentrated under reduced pressure. Ether (200 mL) was added, and the mixture was filtered again and finally evaporated to dryness to yield the title compound. The heterogenous mixture was refluxed for 4 hrs filtered concentrated under reduced pressure Ether (200 mL) was added the mixture was filtered again finally evaporated to dryness

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1-Bromo-3-methylsulfanyl-benzene (5.0 g, 24.6 mmol) was dissolved in dry THF (40 ml) and cooled to −78° C. under a stream of Argon (g). n-BuLi (12.8 ml, 2.5 M in hexane, 31.9 mmol) was added dropwise via syringe and the reaction mixture was stirred for an additional 30 min at −78° C., then the temperature was increased to 0° C. for 5 min and then decreased to −78° C. 1-tert-Butoxycarbonyl-4-piperidone (5.4 g, 27.06 mmol) dissolved in dry THF (30 ml) was added via syringe. The reaction mixture was allowed to reach room temperature and then stirred for 1 hour, and finally quenched with saturated ammonium chloride solution (30 ml). The mixture was extracted several times with EtOAc and the combined organic phases were dried (MgSO4), filtered and evaporated to dryness. The oily residue was chromatho-graphed on a silica column using CH2Cl2:MeOH (19:1 (v/v)) as eluent, yielded 4-hydroxy-4-(3-methylsulfanyl-phenyl)-piperidin-1-carboxylic acid tert-butyl ester (6 g, 76%). MS m/z (relative intensity, 70 eV) 323.1 (M+, 6), 223.0 (11), 178.0 (7), 152 (3), 57.0 (bp), 56 (30). the temperature was increased to 0° C. for 5 min decreased to −78° C was added via syringe to reach room temperature stirred for 1 hour finally quenched with saturated ammonium chloride solution (30 ml) The mixture was extracted several times with EtOAc the combined organic phases were dried (MgSO4) filtered evaporated to dryness

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

Procedure: 3-Bromothioanisole was dissolved in methanol (20 ml) and cooled to 0° C. (ice/water bath). A solution of Oxone® (9.22 g) in water (30 ml) was added to this and the resultant cloudy slurry was stirred at room temperature for 3 hours. The reaction mixture was diluted with water and product extracted with dichloromethane. The combined fractions of dichloromethane were washed with brine and dried over anhydrous magnesium sulfate. After filtration, solvent was removed by evaporation under reduced pressure to give the sub-title compound as a solid (1.02 g). extracted with dichloromethane The combined fractions of dichloromethane were washed with brine dried over anhydrous magnesium sulfate After filtration, solvent was removed by evaporation under reduced pressure

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

Procedure: To a solution of 3-bromothiophenol (10 g) in acetone (250 mL) was added potassium carbonate (14.6 g) and iodomethane (4.28 mL). The heterogenous mixture was refluxed for 4 hrs., cooled to room temperature, filtered, and concentrated under reduced pressure. Ether (200 mL) was added, and the mixture was filtered again and finally evaporated to dryness to yield the title compound. The heterogenous mixture was refluxed for 4 hrs filtered concentrated under reduced pressure Ether (200 mL) was added the mixture was filtered again finally evaporated to dryness

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3-Bromothioanisol (0.5 g, 2.46 mmol) was added to methylene chloride (12 mL) and chilled to 0° C. To this was added 3-chloroperoxybenzoic acid (0.467 g, 2.71 mmol). The m-CPBA did not dissolve completely. The mixture was stirred overnight. The reaction was quenched with a saturated sodium thiosulfate (30 mL) solution. The product was extracted with EtOAc (3×20 mL). The organic fractions were combined, washed with brine (20 mL), and dried with sodium sulfate. The organic was then concentrated to yield 0.912 g (81%) 1-bromo-3-methanesulfinyl-benzene. 1HNMR (methylene chloride-d2) δ 7.83 (t, J=2.0 Hz, 1H), 7.66 (d, J=7.6 Hz, 1H), 7.57 (d, J=8.3 Hz, 1H), 7.44 (t, J=7.9 Hz, 1H), 2.77 (s, 3H); LC-MS RT: 1.28, [M+H]+: 219.0. The reaction was quenched with a saturated sodium thiosulfate (30 mL) solution The product was extracted with EtOAc (3×20 mL) washed with brine (20 mL) dried with sodium sulfate The organic was then concentrated

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

Procedure: To a solution of 3-bromothiophenol (10 g) in acetone (250 mL) was added potassium carbonate (14.6 g) and iodomethane (4.28 mL). The heterogenous mixture was refluxed for 4 hrs., cooled to room temperature, filtered, and concentrated under reduced pressure. Ether (200 mL) was added, and the mixture was filtered again and finally evaporated to dryness to yield the title compound. The heterogenous mixture was refluxed for 4 hrs filtered concentrated under reduced pressure Ether (200 mL) was added the mixture was filtered again finally evaporated to dryness