(3,5-dibromophenyl)methanol

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

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

Procedure: To a cooled (dry ice) mixture of 3,5-dibromobenzyl alcohol (1 g, 3.8 mmol) and PdCl2(dppf) [0.07 eq] in dry THF (10 mL) was added 1.1 M Et2Zn (15 mL, 16 mmol, 4.4 eq). The resulting mixture was allowed to warm to RT, stirred at 45° C. (programmed block temperature, overnight). To bring the reaction to completion (disappearance of both starting material and monoalkylated product) additional 1.1 M Et2Zn (10 mL, 11 mmol, 2.9 eq) was added with continued stirring at 45° C. (again overnight). After cooling, the reaction mixture was then added to a stirred mixture of dilute HCl and heptane/EtOAc (2:1; ˜200 mL), and the organic layer was dried (Na2SO4), filtered, and evaporated. Chromatography (10% EtOAc/heptane) gave 0.33 g (yield of 53%) of title product. 1H NMR (300 MHz, CDCl3) δ 1.22 (t, 6H), 1.65 (br s, 1H), 2.61 (q, 4H), 4.66 (s, 2H), 6.95-7.05 (m, 3H). To a cooled was added with continued stirring at 45° C. (again overnight) After cooling the organic layer was dried (Na2SO4) filtered evaporated

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

Procedure: Sodium borohydride (0.75 g) was added portionwise to a stirred suspension of 3,5-dibromobenzaldehyde (10.46 g) in methanol (50 ml) at 0° C. The mixture was stirred at 0° C. for 30 minutes, allowed to warm to room temperature and then its pH was adjusted to 2 using concentrated hydrochloric acid. Evaporation under vacuum provided a residue which was partitioned between ethyl acetate and water. The organic phase was washed with water, dried(MgSO4), then evaporated under vacuum to furnish the title compound as a solid (10.0 g), m.p. 103°-104° C. Found: C, 31.98; H, 2.23. C7H6Br2O requires C, 31.61; H, 2.77%. to warm to room temperature Evaporation under vacuum provided a residue which was partitioned between ethyl acetate and water The organic phase was washed with water, dried(MgSO4) evaporated under vacuum

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

Procedure: Sodium borohydride (0.75 g) was added portionwise to a stirred suspension of 3,5-dibromobenzaldehyde (10.46 g) in methanol (50 ml) at 0° C. The mixture was stirred at 0° C. for 30 minutes, allowed to warm to room temperature and then its pH was adjusted to 2 using concentrated hydrochloric acid. Evaporation under vacuum provided a residue which was partitioned between ethyl acetate and water. The organic phase was washed with water, dried(MgSO4), then evaporated under vacuum to furnish the title compound as a solid (10.0 g), m.p. 103°-104° C. Found: C, 31.98; H, 2.23. C7H6Br2O requires C, 31.61; H, 2.77%. to warm to room temperature Evaporation under vacuum provided a residue which was partitioned between ethyl acetate and water The organic phase was washed with water, dried(MgSO4) evaporated under vacuum

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

Procedure: To a cooled (dry ice) mixture of 3,5-dibromobenzyl alcohol (1 g, 3.8 mmol) and PdCl2(dppf) [0.07 eq] in dry THF (10 mL) was added 1.1 M Et2Zn (15 mL, 16 mmol, 4.4 eq). The resulting mixture was allowed to warm to RT, stirred at 45° C. (programmed block temperature, overnight). To bring the reaction to completion (disappearance of both starting material and monoalkylated product) additional 1.1 M Et2Zn (10 mL, 11 mmol, 2.9 eq) was added with continued stirring at 45° C. (again overnight). After cooling, the reaction mixture was then added to a stirred mixture of dilute HCl and heptane/EtOAc (2:1; ˜200 mL), and the organic layer was dried (Na2SO4), filtered, and evaporated. Chromatography (10% EtOAc/heptane) gave 0.33 g (yield of 53%) of title product. 1H NMR (300 MHz, CDCl3) δ 1.22 (t, 6H), 1.65 (br s, 1H), 2.61 (q, 4H), 4.66 (s, 2H), 6.95-7.05 (m, 3H). To a cooled was added with continued stirring at 45° C. (again overnight) After cooling the organic layer was dried (Na2SO4) filtered evaporated

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

Procedure: To a cooled (dry ice) mixture of 3,5-dibromobenzyl alcohol (1 g, 3.8 mmol) and PdCl2(dppf) [0.07 eq] in dry THF (10 mL) was added 1.1 M Et2Zn (15 mL, 16 mmol, 4.4 eq). The resulting mixture was allowed to warm to RT, stirred at 45° C. (programmed block temperature, overnight). To bring the reaction to completion (disappearance of both starting material and monoalkylated product) additional 1.1 M Et2Zn (10 mL, 11 mmol, 2.9 eq) was added with continued stirring at 45° C. (again overnight). After cooling, the reaction mixture was then added to a stirred mixture of dilute HCl and heptane/EtOAc (2:1; ˜200 mL), and the organic layer was dried (Na2SO4), filtered, and evaporated. Chromatography (10% EtOAc/heptane) gave 0.33 g (yield of 53%) of title product. 1H NMR (300 MHz, CDCl3) δ 1.22 (t, 6H), 1.65 (br s, 1H), 2.61 (q, 4H), 4.66 (s, 2H), 6.95-7.05 (m, 3H). To a cooled was added with continued stirring at 45° C. (again overnight) After cooling the organic layer was dried (Na2SO4) filtered evaporated

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

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

Procedure: 3,5-Dibromobenzaldehyde (1.7 g, 6.3 mmol) was dissolved in methanol (100 mL) and sodium borohydride (0.250 g, 6.3 mmol) was added at 0° C. The reaction mixture was stirred for 0.5 h at 0° C. and then at 20° C. for another 0.5 h. The reaction mixture was concentrated in vacuo, diluted with brine (250 mL), acidified with hydrochloric acid and extracted with dichloromethane (3×50 mL). Evaporation of the organic solution gave 3,5-dibromo-benzyl alcohol as a white crystalline compound. at 20° C. for another 0.5 h The reaction mixture was concentrated in vacuo diluted with brine (250 mL) extracted with dichloromethane (3×50 mL) Evaporation of the organic solution

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

Procedure: With stirring, imidazole (1.1 g, 16.0 mmol) is added to a solution of 3,5-dibromobenzyl alcohol (2.8 g, 10.5 mmol) in absolute DMF (20 ml), and the mixture is cooled to 0° C. tert-Butyldiphenylsilyl chloride (3.3 ml, 17.8 mmol) is added dropwise to the reaction solution, which is then stirred at 0° C. for 2 h. The mixture is then warmed to RT and stirred for another 2 h. The reaction mixture is diluted with ethyl acetate (20 ml) and extracted with a semisaturated aqueous NH4Cl solution (20 ml). The organic phase is dried over MgSO4, filtered off and concentrated under reduced pressure. Further purification is carried out by chromatography [PE/EA (99:1)] on a silica gel column. This gives the title compound (5.0 g) as a colorless solid. TLC, silica gel (glass plates), [petroleum ether/ethyl acetate (99:1)], Rf=0.8. is added dropwise to the reaction solution, which is then stirred at 0° C. for 2 h stirred for another 2 h extracted with a semisaturated aqueous NH4Cl solution (20 ml) The organic phase is dried over MgSO4 filtered off concentrated under reduced pressure Further purification

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

Procedure: With stirring, imidazole (1.1 g, 16.0 mmol) is added to a solution of 3,5-dibromobenzyl alcohol (2.8 g, 10.5 mmol) in absolute DMF (20 ml), and the mixture is cooled to 0° C. tert-Butyldiphenylsilyl chloride (3.3 ml, 17.8 mmol) is added dropwise to the reaction solution, which is then stirred at 0° C. for 2 h. The mixture is then warmed to RT and stirred for another 2 h. The reaction mixture is diluted with ethyl acetate (20 ml) and extracted with a semisaturated aqueous NH4Cl solution (20 ml). The organic phase is dried over MgSO4, filtered off and concentrated under reduced pressure. Further purification is carried out by chromatography [PE/EA (99:1)] on a silica gel column. This gives the title compound (5.0 g) as a colorless solid. TLC, silica gel (glass plates), [petroleum ether/ethyl acetate (99:1)], Rf=0.8. is added dropwise to the reaction solution, which is then stirred at 0° C. for 2 h stirred for another 2 h extracted with a semisaturated aqueous NH4Cl solution (20 ml) The organic phase is dried over MgSO4 filtered off concentrated under reduced pressure Further purification

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

Procedure: Sodium borohydride (0.75 g) was added portionwise to a stirred suspension of 3,5-dibromobenzaldehyde (10.46 g) in methanol (50 ml) at 0° C. The mixture was stirred at 0° C. for 30 minutes, allowed to warm to room temperature and then its pH was adjusted to 2 using concentrated hydrochloric acid. Evaporation under vacuum provided a residue which was partitioned between ethyl acetate and water. The organic phase was washed with water, dried (MgSO4), then evaporated under vacuum to furnish the title compound as a solid (10.0 g), m.p. 103°-104° C. Found: C,31.98; H,2.23. C7H6Br2O requires C,31.61; H,2.77%. to warm to room temperature Evaporation under vacuum provided a residue which was partitioned between ethyl acetate and water The organic phase was washed with water dried (MgSO4) evaporated under vacuum

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

Procedure: To a cooled (dry ice) mixture of 3,5-dibromobenzyl alcohol (1 g, 3.8 mmol) and PdCl2(dppf)[0.07 eq] in dry THF (10 mL) was added 1.1 M Et2Zn (15 mL, 16 mmol, 4.4 eq). The resulting mixture was allowed to warm to RT, stirred at 45° C. (programmed block temperature, overnight). To bring the reaction to completion (disappearance of both starting material and monoalkylated product) additional 1.1 M Et2Zn (10 mL, 11 mmol, 2.9 eq) was added with continued stirring at 45° C. (again overnight). After cooling, the reaction mixture was then added to a stirred mixture of dilute HCl and heptane/EtOAc (2:1; ˜200 mL), and the organic layer was dried (Na2SO4), filtered, and evaporated. Chromatography (10% EtOAc/heptane) gave 0.33 g (yield of 53%) of title product. 1H NMR (300 MHz, CDCl3) δ 1.22 (t, 6H), 1.65 (br s, 1H), 2.61 (q, 4H), 4.66 (s, 2H), 6.95-7.05 (m, 3H). To a cooled was added with continued stirring at 45° C. (again overnight) After cooling the organic layer was dried (Na2SO4) filtered evaporated