3-[tert-butyl(dimethyl)silyl]oxycyclohexan-1-ol

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 37.6 g (3-benzyloxy-phenoxy)-tert-butyl-dimethyl-silane and 3.8 g of Nishimura's catalyst in 200 ml of ethanol was hydrogenated at rt under 50 psi for 6 hours. The reaction mixture was filtered and the filtrate concentrated. The reaction mixture was filtered the filtrate concentrated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The title compound was prepared in 35% yield from 1,3-cyclohexanediol by a procedure analogous to Intermediate 28, Step A. 1H NMR (300 MHz, CDCl3): δ 4.0-4.2 (m, 1H), 3.8-3.95 (m, 1H), 1.3-2.4 (m, 9H), 0.86 (s, 9H), 0.05 (s, 6H).

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 3-(tert-butyldimethylsilyl)oxy-1-cyclohexanol (12.5 g) and triethylamine (9.8 ml) in dichloromethane (200 ml) was added dropwise methylsulfonyl -chloride (4.6 ml) at 5° C. under nitrogen atmosphere. A reaction mixture was allowed to warm to ambient temperature and stirred or 2 hours. Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which was dissolved in ethyl acetate (200 ml) and washed in turn with 1N-aqueous hydrochloric acid (50 ml×2), saturated sodium hydrogen carbonate in water (50 ml×2) and saturated sodium chloride in water (50 ml×2), and dried over magnesium sulfate. Evaporation of the solvent gave a residue, which was chromatographed on silica gel (300 ml) eluting with 10% ethyl acetate in n-hexane to give 3-(tert-butyldimethylsilyl)oxy-1-(methylsulfonyloxy)-cyclohexane(cis and trans mixture, 16.0 g). Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which washed in turn with 1N-aqueous hydrochloric acid (50 ml×2), saturated sodium hydrogen carbonate in water (50 ml×2) and saturated sodium chloride in water (50 ml×2) dried over magnesium sulfate Evaporation of the solvent gave a residue, which was chromatographed on silica gel (300 ml) eluting with 10% ethyl acetate in n-hexane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 3-(tert-butyldimethylsilyl)oxy-1-cyclohexanol (12.5 g) and triethylamine (9.8 ml) in dichloromethane (200 ml) was added dropwise methylsulfonyl -chloride (4.6 ml) at 5° C. under nitrogen atmosphere. A reaction mixture was allowed to warm to ambient temperature and stirred or 2 hours. Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which was dissolved in ethyl acetate (200 ml) and washed in turn with 1N-aqueous hydrochloric acid (50 ml×2), saturated sodium hydrogen carbonate in water (50 ml×2) and saturated sodium chloride in water (50 ml×2), and dried over magnesium sulfate. Evaporation of the solvent gave a residue, which was chromatographed on silica gel (300 ml) eluting with 10% ethyl acetate in n-hexane to give 3-(tert-butyldimethylsilyl)oxy-1-(methylsulfonyloxy)-cyclohexane(cis and trans mixture, 16.0 g). Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which washed in turn with 1N-aqueous hydrochloric acid (50 ml×2), saturated sodium hydrogen carbonate in water (50 ml×2) and saturated sodium chloride in water (50 ml×2) dried over magnesium sulfate Evaporation of the solvent gave a residue, which was chromatographed on silica gel (300 ml) eluting with 10% ethyl acetate in n-hexane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 1,3-cyclohexanediol (cis and trans mixture, 25 g) and imidazole (8.8 g) in a mixture of dichloromethane (150 ml) and tetrahydrofuran (150 ml) was added dropwise a solution of tert-butyldimethylsilyl chloride (16.2 g) in a mixture of dichloromethane (40 ml) and tetrahydrofuran (40 ml) at 0° C. A reaction mixture was allowed to warm to ambient temperature and stirred overnight. Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which was dissolved in ethyl acetate (300 ml) and washed in turn with 1N aqueous hydrochloric acid (100 ml), brine (100 ml), saturated sodium hydrogen carbonate in water (100 ml), and saturated sodium chloride in water, and dried over magnesium sulfate. Evaporation of the solvent gave a residue, which was chromatographed on silica gel (500 ml) eluting in turn with 10% and 20% ethyl acetate in n-hexane to give 3-(tert-butyldimethylsilyl)oxy-1-cyclohexanol (cis and. trans mixture) (12.52 g). Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which washed in turn with 1N aqueous hydrochloric acid (100 ml), brine (100 ml), saturated sodium hydrogen carbonate in water (100 ml), and saturated sodium chloride in water dried over magnesium sulfate Evaporation of the solvent gave a residue, which was chromatographed on silica gel (500 ml) eluting in turn with 10% and 20% ethyl acetate in n-hexane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 1,3-cyclohexanediol (cis and trans mixture, 25 g) and imidazole (8.8 g) in a mixture of dichloromethane (150 ml) and tetrahydrofuran (150 ml) was added dropwise a solution of tert-butyldimethylsilyl chloride (16.2 g) in a mixture of dichloromethane (40 ml) and tetrahydrofuran (40 ml) at 0° C. A reaction mixture was allowed to warm to ambient temperature and stirred overnight. Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which was dissolved in ethyl acetate (300 ml) and washed in turn with 1N aqueous hydrochloric acid (100 ml), brine (100 ml), saturated sodium hydrogen carbonate in water (100 ml), and saturated sodium chloride in water, and dried over magnesium sulfate. Evaporation of the solvent gave a residue, which was chromatographed on silica gel (500 ml) eluting in turn with 10% and 20% ethyl acetate in n-hexane to give 3-(tert-butyldimethylsilyl)oxy-1-cyclohexanol (cis and. trans mixture) (12.52 g). Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which washed in turn with 1N aqueous hydrochloric acid (100 ml), brine (100 ml), saturated sodium hydrogen carbonate in water (100 ml), and saturated sodium chloride in water dried over magnesium sulfate Evaporation of the solvent gave a residue, which was chromatographed on silica gel (500 ml) eluting in turn with 10% and 20% ethyl acetate in n-hexane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 3-(tert-butyldimethylsilyl)oxy-1-cyclohexanol (12.5 g) and triethylamine (9.8 ml) in dichloromethane (200 ml) was added dropwise methylsulfonyl chloride (4.6 ml) at 5° C. under nitrogen atmosphere. A reaction mixture was allowed to warm to ambient temperature and stirred for 2 hours. Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which was dissolved in ethyl acetate (200 ml) and washed in turn with 1N-aqueous hydrochloric acid (50 ml×2), saturated sodium hydrogen carbonate in water (50 ml×2) and saturated sodium chloride in water (50 ml×2), and dried over magnesium sulfate. Evaporation of the solvent gave a residue, which was chromatographed on silica gel (300 ml) eluting with 10% ethyl acetate in n-hexane to give 3-(tert-butyldimethylsilyl)oxy-1-(methylsulfonyloxy)-cyclohexane(cis and trans mixture, 16.0 g). Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which washed in turn with 1N-aqueous hydrochloric acid (50 ml×2), saturated sodium hydrogen carbonate in water (50 ml×2) and saturated sodium chloride in water (50 ml×2) dried over magnesium sulfate Evaporation of the solvent gave a residue, which was chromatographed on silica gel (300 ml) eluting with 10% ethyl acetate in n-hexane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 3-(tert-butyldimethylsilyl)oxy-1-cyclohexanol (12.5 g) and triethylamine (9.8 ml) in dichloromethane (200 ml) was added dropwise methylsulfonyl chloride (4.6 ml) at 5° C. under nitrogen atmosphere. A reaction mixture was allowed to warm to ambient temperature and stirred for 2 hours. Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which was dissolved in ethyl acetate (200 ml) and washed in turn with 1N-aqueous hydrochloric acid (50 ml×2), saturated sodium hydrogen carbonate in water (50 ml×2) and saturated sodium chloride in water (50 ml×2), and dried over magnesium sulfate. Evaporation of the solvent gave a residue, which was chromatographed on silica gel (300 ml) eluting with 10% ethyl acetate in n-hexane to give 3-(tert-butyldimethylsilyl)oxy-1-(methylsulfonyloxy)-cyclohexane(cis and trans mixture, 16.0 g). Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which washed in turn with 1N-aqueous hydrochloric acid (50 ml×2), saturated sodium hydrogen carbonate in water (50 ml×2) and saturated sodium chloride in water (50 ml×2) dried over magnesium sulfate Evaporation of the solvent gave a residue, which was chromatographed on silica gel (300 ml) eluting with 10% ethyl acetate in n-hexane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 1,3-cyclohexanediol (cis and trans mixture, 25 g) and imidazole (8.8 g) in a mixture of dichloromethane (150 ml) and tetrahydrofuran (150 ml) was added dropwise a solution of tert-butyldimethylsilyl chloride (16.2 g) in a mixture of dichloromethane (40 ml) and tetrahydrofuran (40 ml) at 0° C. A reaction mixture was allowed to warm to ambient temperature and stirred overnight. Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which was dissolved in ethyl acetate (300 ml) and washed in turn with 1N-aqueous hydrochloric acid (100 ml), brine (100 ml), saturated sodium hydrogen carbonate in water (100 ml), and saturated sodium chloride in water, and dried over magnesium sulfate. Evaporation of the solvent gave a residue, which was chromatographed on silica gel (500 ml) eluting in turn with 10% and 20% ethyl acetate in n-hexane to give 3-(tert-butyldimethylsilyl)oxy-1-cyclohexanol (cis and trans mixture) (12.52 g). Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which washed in turn with 1N-aqueous hydrochloric acid (100 ml), brine (100 ml), saturated sodium hydrogen carbonate in water (100 ml), and saturated sodium chloride in water dried over magnesium sulfate Evaporation of the solvent gave a residue, which was chromatographed on silica gel (500 ml) eluting in turn with 10% and 20% ethyl acetate in n-hexane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 37.6 g (3-benzyloxy-phenoxy)-tert-butyl-dimethyl-silane and 3.8 g of Nishimura's catalyst in 200 ml of ethanol was hydrogenated at rt under 50 psi for 6 hours. The reaction mixture was filtered and the filtrate concentrated. The reaction mixture was filtered the filtrate concentrated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The title compound was prepared in 35% yield from 1,3-cyclohexanediol by a procedure analogous to Intermediate 28, Step A. 1H NMR (300 MHz, CDCl3): δ 4.0-4.2 (m, 1H), 3.8-3.95 (m, 1H), 1.3-2.4 (m, 9H), 0.86 (s, 9H), 0.05 (s, 6H).

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 3-(tert-butyldimethylsilyl)oxy-1-cyclohexanol (12.5 g) and triethylamine (9.8 ml) in dichloromethane (200 ml) was added dropwise methylsulfonyl -chloride (4.6 ml) at 5° C. under nitrogen atmosphere. A reaction mixture was allowed to warm to ambient temperature and stirred or 2 hours. Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which was dissolved in ethyl acetate (200 ml) and washed in turn with 1N-aqueous hydrochloric acid (50 ml×2), saturated sodium hydrogen carbonate in water (50 ml×2) and saturated sodium chloride in water (50 ml×2), and dried over magnesium sulfate. Evaporation of the solvent gave a residue, which was chromatographed on silica gel (300 ml) eluting with 10% ethyl acetate in n-hexane to give 3-(tert-butyldimethylsilyl)oxy-1-(methylsulfonyloxy)-cyclohexane(cis and trans mixture, 16.0 g). Insoluble material was removed by filtration and mother liquor was concentrated under reduced pressure to give residue, which washed in turn with 1N-aqueous hydrochloric acid (50 ml×2), saturated sodium hydrogen carbonate in water (50 ml×2) and saturated sodium chloride in water (50 ml×2) dried over magnesium sulfate Evaporation of the solvent gave a residue, which was chromatographed on silica gel (300 ml) eluting with 10% ethyl acetate in n-hexane