(4-bromophenoxy)-tert-butyl-dimethylsilane

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

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

Procedure: The title compound was prepared from rac-[(3-fluoro-4-methyl-phenyl)-(methoxy-methyl-carbamoyl)-methyl]-carbamic acid tert-butyl ester (Intermediate 7) and (4-bromo-phenoxy)-tert-butyl-dimethyl-silane in analogy to Example 1a): MS (ISP): 358.3 ((M−Si(CH3)2C(CH3)3)+H)+ (100%).

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

Procedure: The title compound was prepared from rac-[(3-chloro-4-methyl-phenyl)-(methoxy-methyl-carbamoyl)-methyl]-carbamic acid tert-butyl ester (Intermediate 4) and (4-bromo-phenoxy)-tert-butyl-dimethyl-silane in analogy to Example 1a): MS (ISP): 374.3 ((M−Si(CH3)2C(CH3)3)+H)+ (100%).

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

Procedure: The title compound was prepared from rac-[(3,4-dichloro-phenyl)-(methoxy-methyl-carbamoyl)-methyl]-carbamic acid tert-butyl ester (Intermediate 9) and (4-bromo-phenoxy)-tert-butyl-dimethyl-silane in analogy to Example 1a): MS (ISP): 510.3 and 512.2 (M+H)+, 410.1 and 412.1 ((M-Boc)+H)+ (100%).

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

Procedure: The title compound was prepared from rac-[(4-chloro-phenyl)-(methoxy-methyl-carbamoyl)-methyl]-carbamic acid tert-butyl ester (Intermediate 8) and (4-bromo-phenoxy)-tert-butyl-dimethyl-silane in analogy to Example 1a): MS (ISP): 476.0 (M+H)+.

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

Procedure: To a solution of 4-tert-butyldimethylsilyloxybromobenzene (11.49 g) in tetrahydrofuran (100 ml) was added a solution of n-butyllithium in n-hexane (1.59M, 32.7 ml) dropwise at −55° C. under a nitrogen atmosphere, and the mixture was stirred for 1 hour at −60° C. To the reaction mixture was added triisopropyl borate (12.84 ml), and the mixture was stirred at −60° C. for 1 hour. The reaction mixture was warmed to ambient temperature, poured into a saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The separated organic layer was washed with brine, dried over magnesium sulfate and evaporated under reduced pressure. The solid was triturated with n-hexane, filtered and washed with n-hexane to give 4-tert-butyldimethylsilyloxyphenylboronic acid (7.45 g). the mixture was stirred at −60° C. for 1 hour The reaction mixture was warmed to ambient temperature extracted with ethyl acetate The separated organic layer was washed with brine dried over magnesium sulfate evaporated under reduced pressure The solid was triturated with n-hexane filtered washed with n-hexane

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

Procedure: To a solution of 4-bromo-t-butyldimethylsilyloxybenzene (8.3 g; 29 mmol) in THF (60 ml) at -78° C. is added a solution of butyllithium in hexane (14 ml; 35 mmol) over 10 minutes. This is allowed to stir 1 hour and 2-chlorobenzoxazole (4 ml; 35 mmol) is added dropwise over 5 minutes. After stirring 15 minutes, the reaction is allowed to warm to 0° C. and is quenched with MeOH. This is then poured into 1N HCl and after stirring 1 hour is extracted with ethyl acetate. The organic extracts are dried (MgSO4) and then concentrated to yield 4-(benzoxazol-2-yl)phenol which is used directly in Step C. After stirring 15 minutes is quenched with MeOH This is then poured into 1N HCl after stirring 1 hour is extracted with ethyl acetate The organic extracts are dried (MgSO4) concentrated

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

Procedure: To a solution of 4-bromophenol (5.1 g; 29 mmol) and imidazole (2 g; 29 mmol) in CH2Cl2 (50 ml) at 0° C. is added t-butyldimethylsilyl chloride (4.4 g; 29 mmol) and the reaction is stirred for 15 hours. This is then diluted with CH2Cl2, washed with H2O, ammonium chloride solution, NaHCO3, dried (MgSO4) and concentrated in vacuo to yield 4-bromo-t-butyldimethylsilyloxybenzene as an oil which is used directly in Step B without further purification. washed with H2O, ammonium chloride solution, NaHCO3 dried (MgSO4) concentrated in vacuo

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

Procedure: The general procedure of Example 17 was repeated using 4-n-pentyl-4-phenyl-4-silacyclohexanone, 4-bromo-1-(t-butyldimethylsiloxy)benzene and 1-bromo-2,2,2-trifluoroethane, thereby obtaining the intended compound. obtaining the intended compound

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

Procedure: The general procedure of Example 17 was repeated using 4-n-pentyl-4-phenyl-4-silacyclohexanone, 4-bromo-1-(t-butyldimethylsiloxy)benzene and 1-bromo-2,2,2-trifluoroethane, thereby obtaining the intended compound. obtaining the intended compound

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

Procedure: The general procedure of Example 1 was repeated using 1-bromo-4-(t-butyldimethylsiloxy)benzene, 4-(4-n-propyl-4-phenyl-4-silacyclohexyl)cyclohexanone and 1-bromo-3,3,3-trifluoro-n-propane, thereby obtaining the intended compound. obtaining the intended compound

Conditions: temp:-70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A dry reactor equipped with two addition funnels, nitrogen inlet, and a mechanical stirrer was set up over a dry ice bath. To one of the addition funnels was added a filtered, preformed Grignard reagent from the reaction of 4-(t-butyldimethylsilyloxy)-bromobenzene (28.7 g, 0.1 mol) with magnesium turnings (2.96 g, 0.12 mol) in THF (70 mL). To the other addition funnel was added trimethylborate (12.48 g, 0.12 mol) in THF (50 mL). The reactor was charged with about 10 mL of the borate solution and was cooled to -70° C. About 10 mL of the Grignard solution was then added. The remaining borate and Grignard solutions were then added in aliquots in such a way as to ensure a slight excess of borate. The reaction mixture was stirred at -70° C. for one hour then stirred at room temperature for 20 hours. The reactor was cooled to 0° C. and water (100 mL) was slowly added with vigorous stirring. The mixture was extracted with ether (400 mL). The ether layer was washed with water (2×200 mL), dried over anhydrous MgSO4, then concentrated on a roto-evaporator to afford a light-tan-colored solid (22.0 g, 87 percent). 1H and 13C NMR spectra were consistent with the following structure. ##STR11## A dry reactor equipped with two addition funnels, nitrogen inlet, and a mechanical stirrer was set up over a dry ice bath To one of the addition funnels was added a filtered About 10 mL of the Grignard solution was then added then stirred at room temperature for 20 hours The reactor was cooled to 0° C. The mixture was extracted with ether (400 mL) The ether layer was washed with water (2×200 mL) dried over anhydrous MgSO4 concentrated on a roto-evaporator