chloro-hexyl-dimethylsilane

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

Procedure: To the same reactor as used in Example 1 were added 40.1 g (0.25 mole) of hexyldimethylsilanol, 160 g of 1,2-dichloroethane and 1.83 g (0.025 mole) of N,N-dimethylformamide, and 27.2 g (0.275 mole) of phosgene was introduced into the resulting mixture at a temperature of from 40° to 45° C. over 2 hours with stirring. After completion of the introduction, the same procedure as in Example 7 was carried out to obtain 40.7 g of hexyldimethylchlorosilane. was introduced into the resulting mixture at a temperature of from 40° to 45° C. over 2 hours

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

Procedure: The title compound was synthesized in analogy to example 8, intermediate a), from 5-benzyloxy-1-{(S)-1-(tert-butoxycarbonylamino-methyl)-2-[dimethyl-(1,1,2-trimethyl-propyl)-silanyloxy]-ethyl}-1H-indole-2-carboxylic acid ethyl ester to give a mixture of the desired compound and the unprotected hydroxymethyl compound. The mixture was dissolved in N,N-dimethylformamide and 1 equivalent of imidazole was added. At 0° C., 1 equivalent of dimethylhexylsilyl chloride was added and the cooling bath was removed. The reaction mixture was poured on water and was extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate, filtered and evaporated. The residue was purified by column chromatography over silica gel using n-hexane:ethyl acetate (1:2 v/v) as eluant to give the desired product as a light yellow foam (35%). to give a mixture of the desired compound the cooling bath was removed The reaction mixture was poured on water was extracted twice with ethyl acetate The combined organic layers were washed with brine dried over magnesium sulfate filtered evaporated The residue was purified by column chromatography over silica gel

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

Procedure: The title compound was synthesized in analogy to example 8, intermediate a), from 5-benzyloxy-1-{(S)-1-(tert-butoxycarbonylamino-methyl)-2-[dimethyl-(1,1,2-trimethyl-propyl)-silanyloxy]-ethyl}-1H-indole-2-carboxylic acid ethyl ester to give a mixture of the desired compound and the unprotected hydroxymethyl compound. The mixture was dissolved in N,N-dimethylformamide and 1 equivalent of imidazole was added. At 0° C., 1 equivalent of dimethylhexylsilyl chloride was added and the cooling bath was removed. The reaction mixture was poured on water and was extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate, filtered and evaporated. The residue was purified by column chromatography over silica gel using n-hexane:ethyl acetate (1:2 v/v) as eluant to give the desired product as a light yellow foam (35%). to give a mixture of the desired compound the cooling bath was removed The reaction mixture was poured on water was extracted twice with ethyl acetate The combined organic layers were washed with brine dried over magnesium sulfate filtered evaporated The residue was purified by column chromatography over silica gel

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

Procedure: 3-Bromophenethyl alcohol (46.0 g, 228.78 mmol) was combined with dimethylaminopyridine (6.99 g, 57.19 mmol) and triethylamine (34.73 g, 343.17 mmol) in anhydrous CH2Cl2 (200 mL) and cooled to 0° C. Dimethylhexylsilyl chloride (44.18 g, 247.08 mmol) was added dropwise over ten minutes, then the reaction mixture was warmed to room temperature and stirred for sixteen hours. The reaction mixture was diluted with hexane (800 mL) and filtered. The filtrate was concentrated and the residue was partitioned between ether (800 mL) and 0.3N aqueous HCl (2 times with 400 mL), saturated aqueous NaHCO3 (400 mL), dried (MgSO4) and concentrated. The crude liquid was chromatographed on a silica gel column and eluted with 20% ether in hexane to give title compound (74.45 g, 95%) as a clear liquid. the reaction mixture was warmed to room temperature filtered The filtrate was concentrated the residue was partitioned between ether (800 mL) and 0.3N aqueous HCl (2 times with 400 mL), saturated aqueous NaHCO3 (400 mL) dried (MgSO4) concentrated The crude liquid was chromatographed on a silica gel column eluted with 20% ether in hexane

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

Procedure: 3-Bromophenethyl alcohol (46.0 g, 228.78 mmol) was combined with dimethylaminopyridine (6.99 g, 57.19 mmol) and triethylamine (34.73 g, 343.17 mmol) in anhydrous CH2Cl2 (200 mL) and cooled to 0° C. Dimethylhexylsilyl chloride (44.18 g, 247.08 mmol) was added dropwise over ten minutes, then the reaction mixture was warmed to room temperature and stirred for sixteen hours. The reaction mixture was diluted with hexane (800 mL) and filtered. The filtrate was concentrated and the residue was partitioned between ether (800 mL) and 0.3N aqueous HCl (2 times with 400 mL), saturated aqueous NaHCO3 (400 mL), dried (MgSO4) and concentrated. The crude liquid was chromatographed on a silica gel column and eluted with 20% ether in hexane to give title compound (74.45 g, 95%) as a clear liquid. the reaction mixture was warmed to room temperature filtered The filtrate was concentrated the residue was partitioned between ether (800 mL) and 0.3N aqueous HCl (2 times with 400 mL), saturated aqueous NaHCO3 (400 mL) dried (MgSO4) concentrated The crude liquid was chromatographed on a silica gel column eluted with 20% ether in hexane

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

Procedure: The title compound was synthesized in analogy to example 8, intermediate a), from 5-benzyloxy-1-{(S)-1-(tert-butoxycarbonylamino-methyl)-2-[dimethyl-(1,1,2-trimethyl-propyl)-silanyloxy]-ethyl}-1H-indole-2-carboxylic acid ethyl ester to give a mixture of the desired compound and the unprotected hydroxymethyl compound. The mixture was dissolved in N,N-dimethylformamide and 1 equivalent of imidazole was added. At 0° C., 1 equivalent of dimethylhexylsilyl chloride was added and the cooling bath was removed. The reaction mixture was poured on water and was extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate, filtered and evaporated. The residue was purified by column chromatography over silica gel using n-hexane:ethyl acetate (1:2 v/v) as eluant to give the desired product as a light yellow foam (35%). to give a mixture of the desired compound the cooling bath was removed The reaction mixture was poured on water was extracted twice with ethyl acetate The combined organic layers were washed with brine dried over magnesium sulfate filtered evaporated The residue was purified by column chromatography over silica gel

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

Procedure: 3-Bromophenethyl alcohol (46.0 g, 228.78 mmol) was combined with dimethylaminopyridine (6.99 g, 57.19 mmol) and triethylamine (34.73 g, 343.17 mmol) in anhydrous CH2Cl2 (200 mL) and cooled to 0° C. Dimethylhexylsilyl chloride (44.18 g, 247.08 mmol) was added dropwise over ten minutes, then the reaction mixture was warmed to room temperature and stirred for sixteen hours. The reaction mixture was diluted with hexane (800 mL) and filtered. The filtrate was concentrated and the residue was partitioned between ether (800 mL) and 0.3N aqueous HCl (2 times with 400 mL), saturated aqueous NaHCO3 (400 mL), dried (MgSO4) and concentrated. The crude liquid was chromatographed on a silica gel column and eluted with 20% ether in hexane to give title compound (74.45 g, 95%) as a clear liquid. the reaction mixture was warmed to room temperature filtered The filtrate was concentrated the residue was partitioned between ether (800 mL) and 0.3N aqueous HCl (2 times with 400 mL), saturated aqueous NaHCO3 (400 mL) dried (MgSO4) concentrated The crude liquid was chromatographed on a silica gel column eluted with 20% ether in hexane

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

Procedure: 3-Bromophenethyl alcohol (46.0 g, 228.78 mmol) was combined with dimethylaminopyridine (6.99 g, 57.19 mmol) and triethylamine (34.73 g, 343.17 mmol) in anhydrous CH2Cl2 (200 mL) and cooled to 0° C. Dimethylhexylsilyl chloride (44.18 g, 247.08 mmol) was added dropwise over ten minutes, then the reaction mixture was warmed to room temperature and stirred for sixteen hours. The reaction mixture was diluted with hexane (800 mL) and filtered. The filtrate was concentrated and the residue was partitioned between ether (800 mL) and 0.3N aqueous HCl (2 times with 400 mL), saturated aqueous NaHCO3 (400 mL), dried (MgSO4) and concentrated. The crude liquid was chromatographed on a silica gel column and eluted with 20% ether in hexane to give title compound (74.45 g, 95%) as a clear liquid. the reaction mixture was warmed to room temperature filtered The filtrate was concentrated the residue was partitioned between ether (800 mL) and 0.3N aqueous HCl (2 times with 400 mL), saturated aqueous NaHCO3 (400 mL) dried (MgSO4) concentrated The crude liquid was chromatographed on a silica gel column eluted with 20% ether in hexane

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

Procedure: To the same reactor as used in Example 1 were added 40.1 g (0.25 mole) of hexyldimethylsilanol, 160 g of 1,2-dichloroethane and 1.83 g (0.025 mole) of N,N-dimethylformamide, and 27.2 g (0.275 mole) of phosgene was introduced into the resulting mixture at a temperature of from 40° to 45° C. over 2 hours with stirring. After completion of the introduction, the same procedure as in Example 7 was carried out to obtain 40.7 g of hexyldimethylchlorosilane. was introduced into the resulting mixture at a temperature of from 40° to 45° C. over 2 hours

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

Procedure: 3-Bromophenethyl alcohol (46.0 g, 228.78 mmol) was combined with dimethylaminopyridine (6.99 g, 57.19 mmol) and triethylamine (34.73 g, 343.17 mmol) in anhydrous CH2Cl2 (200 mL) and cooled to 0° C. Dimethylhexylsilyl chloride (44.18 g, 247.08 mmol) was added dropwise over ten minutes, then the reaction mixture was warmed to room temperature and stirred for sixteen hours. The reaction mixture was diluted with hexane (800 mL) and filtered. The filtrate was concentrated and the residue was partitioned between ether (800 mL) and 0.3N aqueous HCl (2 times with 400 mL), saturated aqueous NaHCO3 (400 mL), dried (MgSO4) and concentrated. The crude liquid was chromatographed on a silica gel column and eluted with 20% ether in hexane to give title compound (74.45 g, 95%) as a clear liquid. the reaction mixture was warmed to room temperature filtered The filtrate was concentrated the residue was partitioned between ether (800 mL) and 0.3N aqueous HCl (2 times with 400 mL), saturated aqueous NaHCO3 (400 mL) dried (MgSO4) concentrated The crude liquid was chromatographed on a silica gel column eluted with 20% ether in hexane