[2-[tert-butyl(dimethyl)silyl]oxyphenyl]methanol

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

Procedure: To a solution of triphenylphosphine (39.5 g, 0.15 mol), (2-((tert-butyldimethylsilyl)-oxy)phenyl)methanol (Ia) (12.23 g, 0.05 mol) and imidazole (10.5 g, 0.15 mol) in acetonitrile and diethyl ether (500 ml, CH3CN/Et2O=1:3, v/v) was added bromine (7.7 mL, 0.15 mol) dropwise at 0° C. with stirring. The reaction mixture was stirred at 0° C. for 20 minutes, during which time a white solid precipitated. The solution was carefully decanted and washed with brine (100 mL). The remaining solid was washed with diethyl ether (2×160 mL). All of the organic solutions were combined and concentrated. Hexane (200 ml) was added to the residue, and the solid was removed by filtration. The hexane solution was concentrated to provide the crude product. The product was purified by vacuum distillation (66-68° C. 0.093 Torr) reduced distillation to provide compound IIa (10.4 g, 67%) as a colorless oil. The reaction mixture was stirred at 0° C. for 20 minutes, during which time a white solid precipitated The solution was carefully decanted washed with brine (100 mL) The remaining solid was washed with diethyl ether (2×160 mL) concentrated Hexane (200 ml) was added to the residue the solid was removed by filtration The hexane solution was concentrated

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

Procedure: To a solution of triphenylphosphine (39.5 g, 0.15 mol), (2-((tert-butyldimethylsilyl)-oxy)phenyl)methanol (Ia) (12.23 g, 0.05 mol) and imidazole (10.5 g, 0.15 mol) in acetonitrile and diethyl ether (500 ml, CH3CN/Et2O=1:3, v/v) was added bromine (7.7 mL, 0.15 mol) dropwise at 0° C. with stirring. The reaction mixture was stirred at 0° C. for 20 minutes, during which time a white solid precipitated. The solution was carefully decanted and washed with brine (100 mL). The remaining solid was washed with diethyl ether (2×160 mL). All of the organic solutions were combined and concentrated. Hexane (200 ml) was added to the residue, and the solid was removed by filtration. The hexane solution was concentrated to provide the crude product. The product was purified by vacuum distillation (66-68° C. 0.093 Torr) reduced distillation to provide compound IIa (10.4 g, 67%) as a colorless oil. The reaction mixture was stirred at 0° C. for 20 minutes, during which time a white solid precipitated The solution was carefully decanted washed with brine (100 mL) The remaining solid was washed with diethyl ether (2×160 mL) concentrated Hexane (200 ml) was added to the residue the solid was removed by filtration The hexane solution was concentrated

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

Procedure: The alcohol 29 (135 mg, 0.56 mmol) is dissolved in ethyl acetate (0.82 ml). Pyridine (0.081 ml) is then added, followed by 4-nitrophenyl chloroformate (275 mg, 2.4 eq.). After one night at room temperature, the solvent is evaporated off. Chromatography on silica gel gives the carbonate 30 (206 mg, 91%). After one night at room temperature the solvent is evaporated off

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

Procedure: A solution of 28 (200 mg) in methanol (5.5 ml) containing NaBH4 (28 mg) is stirred for 1 hour at room temperature. 29 (140 mg, 68%) is obtained after hydrolysis and customary extraction.

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

Procedure: [2-(Bromomethyl)phenoxy](tert-butyl)dimethylsilane was prepared according to the literature procedure (J. Chem. Soc. Perkin Trans.1; 1988; 1417). To a solution of (2-([tert-butyl(dimethyl)silyl]oxy}phenyl)methanol (9.9 g/41.5 mmol) in acetonitrile (200 ml) was added carbon tetrabromide (14.5 g/43.6 mmol), triphenylphosphine (11.4 g/43.6 mmol) successively at 0° C., and then the resulting solution was stirred at room temperature for 16 hours. The solvent was evaporated. The residue was purified by column chromatography (SiO2, 200-350 mesh/hexane:ethyl acetate=100:1-20:1-10:1) to afford a colorless oil (12.0 g/96%). The solvent was evaporated The residue was purified by column chromatography (SiO2, 200-350 mesh/hexane:ethyl acetate=100:1-20:1-10:1) to afford a colorless oil (12.0 g/96%)

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

Procedure: To a solution of triphenylphosphine (39.5 g, 0.15 mol), (2-((tert-butyldimethylsilyl)-oxy)phenyl)methanol (Ia) (12.23 g, 0.05 mol) and imidazole (10.5 g, 0.15 mol) in acetonitrile and diethyl ether (500 ml, CH3CN/Et2O=1:3, v/v) was added bromine (7.7 mL, 0.15 mol) dropwise at 0° C. with stirring. The reaction mixture was stirred at 0° C. for 20 minutes, during which time a white solid precipitated. The solution was carefully decanted and washed with brine (100 mL). The remaining solid was washed with diethyl ether (2×160 mL). All of the organic solutions were combined and concentrated. Hexane (200 ml) was added to the residue, and the solid was removed by filtration. The hexane solution was concentrated to provide the crude product. The product was purified by vacuum distillation (66-68° C. 0.093 Torr) reduced distillation to provide compound IIa (10.4 g, 67%) as a colorless oil. The reaction mixture was stirred at 0° C. for 20 minutes, during which time a white solid precipitated The solution was carefully decanted washed with brine (100 mL) The remaining solid was washed with diethyl ether (2×160 mL) concentrated Hexane (200 ml) was added to the residue the solid was removed by filtration The hexane solution was concentrated

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

Procedure: The alcohol 29 (135 mg, 0.56 mmol) is dissolved in ethyl acetate (0.82 ml). Pyridine (0.081 ml) is then added, followed by 4-nitrophenyl chloroformate (275 mg, 2.4 eq.). After one night at room temperature, the solvent is evaporated off. Chromatography on silica gel gives the carbonate 30 (206 mg, 91%). After one night at room temperature the solvent is evaporated off

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

Procedure: A solution of 28 (200 mg) in methanol (5.5 ml) containing NaBH4 (28 mg) is stirred for 1 hour at room temperature. 29 (140 mg, 68%) is obtained after hydrolysis and customary extraction.

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

Procedure: [2-(Bromomethyl)phenoxy](tert-butyl)dimethylsilane was prepared according to the literature procedure (J. Chem. Soc. Perkin Trans.1; 1988; 1417). To a solution of (2-([tert-butyl(dimethyl)silyl]oxy}phenyl)methanol (9.9 g/41.5 mmol) in acetonitrile (200 ml) was added carbon tetrabromide (14.5 g/43.6 mmol), triphenylphosphine (11.4 g/43.6 mmol) successively at 0° C., and then the resulting solution was stirred at room temperature for 16 hours. The solvent was evaporated. The residue was purified by column chromatography (SiO2, 200-350 mesh/hexane:ethyl acetate=100:1-20:1-10:1) to afford a colorless oil (12.0 g/96%). The solvent was evaporated The residue was purified by column chromatography (SiO2, 200-350 mesh/hexane:ethyl acetate=100:1-20:1-10:1) to afford a colorless oil (12.0 g/96%)