tert-butyl 2-trimethylsilylacetate

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

Procedure: A solution of n-butyllithium (2.5M in hexane, 36 ml) was added dropwise with stirring to a cooled solution of diisopropylamine (9.09 g) in dry tetrahydrofuran (i.e. tetrahydofuran) in an atmosphere of nitrogen, whilst maintaining the temperature below -70° C. The mixture was stirred for 0.25 hour and t-butyltrimethylsilylacetate (16.9 g) was added dropwise with stirring whilst maintaining the temperature below -70° C. The mixture was stirred at -78° C. for 1 hour. A suspension of 1-(1-methylcyclopropylcarbonyl)-imidazole (13.5 g) in dry tetrahydrofuran (120 ml) was added dropwise whilst maintaining the temperature below -60° C. The mixture was stirred at -78° C. for 3 hours and the temperature was allowed to rise to room temperature. Hydrochloric acid (2M, 100 ml) was added cautiously and the mixture was extracted with ether (2×100 ml). The combined extracts were washed with hydrochloric acid (2M, 3×50 ml) and water (3×50 ml), dried (anhydrous sodium sulphate) and filtered. The filtrate was evaporated to dryness to give t-butyl 3-(1-methylcyclopropyl)-3-oxopropionate as an orange oil NMR (CDCl3) 0.65(m,2H), 1.1(m,2H), 1.25(s,3H), 1.4(s,9H), 3.2(s,2H). whilst maintaining the temperature below -70° C with stirring whilst maintaining the temperature below -70° C The mixture was stirred at -78° C. for 1 hour was added dropwise whilst maintaining the temperature below -60° C The mixture was stirred at -78° C. for 3 hours to rise to room temperature the mixture was extracted with ether (2×100 ml) The combined extracts were washed with hydrochloric acid (2M, 3×50 ml) and water (3×50 ml) dried (anhydrous sodium sulphate) filtered The filtrate was evaporated to dryness

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

Procedure: A solution of n-butyllithium (2.5M in hexane, 36 ml) was added dropwise with stirring to a cooled solution of diisopropylamine (9.09 g) in dry tetrahydrofuran (i.e. tetrahydofuran) in an atmosphere of nitrogen, whilst maintaining the temperature below -70° C. The mixture was stirred for 0.25 hour and t-butyltrimethylsilylacetate (16.9 g) was added dropwise with stirring whilst maintaining the temperature below -70° C. The mixture was stirred at -78° C. for 1 hour. A suspension of 1-(1-methylcyclopropylcarbonyl)-imidazole (13.5 g) in dry tetrahydrofuran (120 ml) was added dropwise whilst maintaining the temperature below -60° C. The mixture was stirred at -78° C. for 3 hours and the temperature was allowed to rise to room temperature. Hydrochloric acid (2M, 100 ml) was added cautiously and the mixture was extracted with ether (2×100 ml). The combined extracts were washed with hydrochloric acid (2M, 3×50 ml) and water (3×50 ml), dried (anhydrous sodium sulphate) and filtered. The filtrate was evaporated to dryness to give t-butyl 3-(1-methylcyclopropyl)-3-oxopropionate as an orange oil NMR (CDCl3) 0.65(m,2H), 1.1(m,2H), 1.25(s,3H), 1.4(s,9H), 3.2(s,2H). whilst maintaining the temperature below -70° C with stirring whilst maintaining the temperature below -70° C The mixture was stirred at -78° C. for 1 hour was added dropwise whilst maintaining the temperature below -60° C The mixture was stirred at -78° C. for 3 hours to rise to room temperature the mixture was extracted with ether (2×100 ml) The combined extracts were washed with hydrochloric acid (2M, 3×50 ml) and water (3×50 ml) dried (anhydrous sodium sulphate) filtered The filtrate was evaporated to dryness

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

Procedure: A solution of n-butyllithium (2.5M in hexane, 36 ml) was added dropwise with stirring to a cooled solution of diisopropylamine (9.09 g) in dry tetrahydrofuran (i.e. tetrahydofuran) in an atmosphere of nitrogen, whilst maintaining the temperature below -70° C. The mixture was stirred for 0.25 hour and t-butyltrimethylsilylacetate (16.9 g) was added dropwise with stirring whilst maintaining the temperature below -70° C. The mixture was stirred at -78° C. for 1 hour. A suspension of 1-(1-methylcyclopropylcarbonyl)-imidazole (13.5 g) in dry tetrahydrofuran (120 ml) was added dropwise whilst maintaining the temperature below -60° C. The mixture was stirred at -78° C. for 3 hours and the temperature was allowed to rise to room temperature. Hydrochloric acid (2M, 100 ml) was added cautiously and the mixture was extracted with ether (2×100 ml). The combined extracts were washed with hydrochloric acid (2M, 3×50 ml) and water (3×50 ml), dried (anhydrous sodium sulphate) and filtered. The filtrate was evaporated to dryness to give t-butyl 3-(1-methylcyclopropyl)-3-oxopropionate as an orange oil NMR (CDCl3) 0.65(m,2H), 1.1(m,2H), 1.25(s,3H), 1.4(s,9H), 3.2(s,2H). whilst maintaining the temperature below -70° C with stirring whilst maintaining the temperature below -70° C The mixture was stirred at -78° C. for 1 hour was added dropwise whilst maintaining the temperature below -60° C The mixture was stirred at -78° C. for 3 hours to rise to room temperature the mixture was extracted with ether (2×100 ml) The combined extracts were washed with hydrochloric acid (2M, 3×50 ml) and water (3×50 ml) dried (anhydrous sodium sulphate) filtered The filtrate was evaporated to dryness

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of lithium diisopropylamide, afforded by combining 3.4 g of diisopropylamine with 26 ml of n-butyllithium, at -40° C. in THF is added tert-butyl trimethylsilylacetate (8 g, 0.042 mmol) and the mixture stirred for 1 hour. To the reaction mixture is added 2-methylthio-6-n-hexylbenzaldehyde (7.08 g, 0.03 mmol) dropwise and stirred for 2 hours at -40° C. The reaction mixture is allowed to warm to -10° C. and cold lN HCl poured in. The mixture is extracted with diethyl ether. The extracts are washed with water and then brine, dried over MgSO4 and concentrated to afford tert-butyl 2-methylthio-6-n-hexylcinnamate which is hydrolyzed in methylene chloride with trifluoroacetic acid by refluxing overnight to afford the subtitle compound. stirred for 2 hours at -40° C The mixture is extracted with diethyl ether The extracts are washed with water brine, dried over MgSO4 concentrated

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of lithium diisopropylamide, afforded by combining 3.4 g of diisopropylamine with 26 ml of n-butyllithium, at -40° C. in THF is added tert-butyl trimethylsilylacetate (8 g, 0.042 mmol) and the mixture stirred for 1 hour. To the reaction mixture is added 2-methylthio-6-n-hexylbenzaldehyde (7.08 g, 0.03 mmol) dropwise and stirred for 2 hours at -40° C. The reaction mixture is allowed to warm to -10° C. and cold lN HCl poured in. The mixture is extracted with diethyl ether. The extracts are washed with water and then brine, dried over MgSO4 and concentrated to afford tert-butyl 2-methylthio-6-n-hexylcinnamate which is hydrolyzed in methylene chloride with trifluoroacetic acid by refluxing overnight to afford the subtitle compound. stirred for 2 hours at -40° C The mixture is extracted with diethyl ether The extracts are washed with water brine, dried over MgSO4 concentrated

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

Procedure: A solution of n-butyllithium (2.5M in hexane, 36 ml) was added dropwise with stirring to a cooled solution of diisopropylamine (9.09 g) in dry tetrahydrofuran (i.e. tetrahydofuran) in an atmosphere of nitrogen, whilst maintaining the temperature below -70° C. The mixture was stirred for 0.25 hour and t-butyltrimethylsilylacetate (16.9 g) was added dropwise with stirring whilst maintaining the temperature below -70° C. The mixture was stirred at -78° C. for 1 hour. A suspension of 1-(1-methylcyclopropylcarbonyl)-imidazole (13.5 g) in dry tetrahydrofuran (120 ml) was added dropwise whilst maintaining the temperature below -60° C. The mixture was stirred at -78° C. for 3 hours and the temperature was allowed to rise to room temperature. Hydrochloric acid (2M, 100 ml) was added cautiously and the mixture was extracted with ether (2×100 ml). The combined extracts were washed with hydrochloric acid (2M, 3×50 ml) and water (3×50 ml), dried (anhydrous sodium sulphate) and filtered. The filtrate was evaporated to dryness to give t-butyl 3-(1-methylcyclopropyl)-3-oxopropionate as an orange oil NMR (CDCl3) 0.65(m,2H), 1.1(m,2H), 1.25(s,3H), 1.4(s,9H), 3.2(s,2H). whilst maintaining the temperature below -70° C with stirring whilst maintaining the temperature below -70° C The mixture was stirred at -78° C. for 1 hour was added dropwise whilst maintaining the temperature below -60° C The mixture was stirred at -78° C. for 3 hours to rise to room temperature the mixture was extracted with ether (2×100 ml) The combined extracts were washed with hydrochloric acid (2M, 3×50 ml) and water (3×50 ml) dried (anhydrous sodium sulphate) filtered The filtrate was evaporated to dryness

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

Procedure: A solution of n-butyllithium (2.5M in hexane, 36 ml) was added dropwise with stirring to a cooled solution of diisopropylamine (9.09 g) in dry tetrahydrofuran (i.e. tetrahydofuran) in an atmosphere of nitrogen, whilst maintaining the temperature below -70° C. The mixture was stirred for 0.25 hour and t-butyltrimethylsilylacetate (16.9 g) was added dropwise with stirring whilst maintaining the temperature below -70° C. The mixture was stirred at -78° C. for 1 hour. A suspension of 1-(1-methylcyclopropylcarbonyl)-imidazole (13.5 g) in dry tetrahydrofuran (120 ml) was added dropwise whilst maintaining the temperature below -60° C. The mixture was stirred at -78° C. for 3 hours and the temperature was allowed to rise to room temperature. Hydrochloric acid (2M, 100 ml) was added cautiously and the mixture was extracted with ether (2×100 ml). The combined extracts were washed with hydrochloric acid (2M, 3×50 ml) and water (3×50 ml), dried (anhydrous sodium sulphate) and filtered. The filtrate was evaporated to dryness to give t-butyl 3-(1-methylcyclopropyl)-3-oxopropionate as an orange oil NMR (CDCl3) 0.65(m,2H), 1.1(m,2H), 1.25(s,3H), 1.4(s,9H), 3.2(s,2H). whilst maintaining the temperature below -70° C with stirring whilst maintaining the temperature below -70° C The mixture was stirred at -78° C. for 1 hour was added dropwise whilst maintaining the temperature below -60° C The mixture was stirred at -78° C. for 3 hours to rise to room temperature the mixture was extracted with ether (2×100 ml) The combined extracts were washed with hydrochloric acid (2M, 3×50 ml) and water (3×50 ml) dried (anhydrous sodium sulphate) filtered The filtrate was evaporated to dryness

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

Procedure: A solution of n-butyllithium (2.5M in hexane, 36 ml) was added dropwise with stirring to a cooled solution of diisopropylamine (9.09 g) in dry tetrahydrofuran (i.e. tetrahydofuran) in an atmosphere of nitrogen, whilst maintaining the temperature below -70° C. The mixture was stirred for 0.25 hour and t-butyltrimethylsilylacetate (16.9 g) was added dropwise with stirring whilst maintaining the temperature below -70° C. The mixture was stirred at -78° C. for 1 hour. A suspension of 1-(1-methylcyclopropylcarbonyl)-imidazole (13.5 g) in dry tetrahydrofuran (120 ml) was added dropwise whilst maintaining the temperature below -60° C. The mixture was stirred at -78° C. for 3 hours and the temperature was allowed to rise to room temperature. Hydrochloric acid (2M, 100 ml) was added cautiously and the mixture was extracted with ether (2×100 ml). The combined extracts were washed with hydrochloric acid (2M, 3×50 ml) and water (3×50 ml), dried (anhydrous sodium sulphate) and filtered. The filtrate was evaporated to dryness to give t-butyl 3-(1-methylcyclopropyl)-3-oxopropionate as an orange oil NMR (CDCl3) 0.65(m,2H), 1.1(m,2H), 1.25(s,3H), 1.4(s,9H), 3.2(s,2H). whilst maintaining the temperature below -70° C with stirring whilst maintaining the temperature below -70° C The mixture was stirred at -78° C. for 1 hour was added dropwise whilst maintaining the temperature below -60° C The mixture was stirred at -78° C. for 3 hours to rise to room temperature the mixture was extracted with ether (2×100 ml) The combined extracts were washed with hydrochloric acid (2M, 3×50 ml) and water (3×50 ml) dried (anhydrous sodium sulphate) filtered The filtrate was evaporated to dryness

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of diisopropylamine (6.60 mL, 46.6 mmol) in THF (200 mL) at −10° C., was added a solution 2.22M of n-butyllithium (20.4 mL, 44.4 mmol). The solution was stirred 15 min at −10° C., cooled down to −78° C. and tert-butyl 2-trimethylsilylacetate (9.7 mL, 44.4 mmol) in 1 mL of THF was added dropwise. The solution was stirred 15 min at −78° C., and 2-allylcyclohexanone (3.3 mL, 22.2 mmol) was added dropwise. The reaction mixture was stirred 1 h at −78° C. and 3 h at −25° C. It was then quenched with saturated NH4Cl, extracted with ethylacetate, washed with brine, dried and concentrated. Purification by flash chromatography (cyclohexane) gave tert-butyl 2-(2-allylcyclohexylidene)acetate (5.06 g, 96%) as a colorless liquid. 1H NMR (400 MHz, CDCl3) 5.62 (1H, m), 5.41 (1H, s), 4.89 (2H, m), 3.83 (1H, m), 2.16 (3H, m), 1.90 (1H, m), 1.73 (1H, m), 1.61 (1H, m), 1.47-1.22 (4H, m), 1.36 (9H, s). cooled down to −78° C. The solution was stirred 15 min at −78° C. The reaction mixture was stirred 1 h at −78° C. and 3 h at −25° C It was then quenched with saturated NH4Cl extracted with ethylacetate washed with brine dried concentrated Purification by flash chromatography (cyclohexane)

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of diisopropylamine (6.60 mL, 46.6 mmol) in THF (200 mL) at −10° C., was added a solution 2.22M of n-butyllithium (20.4 mL, 44.4 mmol). The solution was stirred 15 min at −10° C., cooled down to −78° C. and tert-butyl 2-trimethylsilylacetate (9.7 mL, 44.4 mmol) in 1 mL of THF was added dropwise. The solution was stirred 15 min at −78° C., and 2-allylcyclohexanone (3.3 mL, 22.2 mmol) was added dropwise. The reaction mixture was stirred 1 h at −78° C. and 3 h at −25° C. It was then quenched with saturated NH4Cl, extracted with ethylacetate, washed with brine, dried and concentrated. Purification by flash chromatography (cyclohexane) gave tert-butyl 2-(2-allylcyclohexylidene)acetate (5.06 g, 96%) as a colorless liquid. 1H NMR (400 MHz, CDCl3) 5.62 (1H, m), 5.41 (1H, s), 4.89 (2H, m), 3.83 (1H, m), 2.16 (3H, m), 1.90 (1H, m), 1.73 (1H, m), 1.61 (1H, m), 1.47-1.22 (4H, m), 1.36 (9H, s). cooled down to −78° C. The solution was stirred 15 min at −78° C. The reaction mixture was stirred 1 h at −78° C. and 3 h at −25° C It was then quenched with saturated NH4Cl extracted with ethylacetate washed with brine dried concentrated Purification by flash chromatography (cyclohexane)

Conditions: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of diisopropylamine (6.60 mL, 46.6 mmol) in THF (200 mL) at −10° C., was added a solution 2.22M of n-butyllithium (20.4 mL, 44.4 mmol). The solution was stirred 15 min at −10° C., cooled down to −78° C. and tert-butyl 2-trimethylsilylacetate (9.7 mL, 44.4 mmol) in 1 mL of THF was added dropwise. The solution was stirred 15 min at −78° C., and 2-allylcyclohexanone (3.3 mL, 22.2 mmol) was added dropwise. The reaction mixture was stirred 1 h at −78° C. and 3 h at −25° C. It was then quenched with saturated NH4Cl, extracted with ethylacetate, washed with brine, dried and concentrated. Purification by flash chromatography (cyclohexane) gave tert-butyl 2-(2-allylcyclohexylidene)acetate (5.06 g, 96%) as a colorless liquid. 1H NMR (400 MHz, CDCl3) 5.62 (1H, m), 5.41 (1H, s), 4.89 (2H, m), 3.83 (1H, m), 2.16 (3H, m), 1.90 (1H, m), 1.73 (1H, m), 1.61 (1H, m), 1.47-1.22 (4H, m), 1.36 (9H, s). cooled down to −78° C. The solution was stirred 15 min at −78° C. The reaction mixture was stirred 1 h at −78° C. and 3 h at −25° C It was then quenched with saturated NH4Cl extracted with ethylacetate washed with brine dried concentrated Purification by flash chromatography (cyclohexane)

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

Procedure: A solution of n-butyllithium (2.5M in hexane, 36 ml) was added dropwise with stirring to a cooled solution of diisopropylamine (9.09 g) in dry tetrahydrofuran (i.e. tetrahydofuran) in an atmosphere of nitrogen, whilst maintaining the temperature below -70° C. The mixture was stirred for 0.25 hour and t-butyltrimethylsilylacetate (16.9 g) was added dropwise with stirring whilst maintaining the temperature below -70° C. The mixture was stirred at -78° C. for 1 hour. A suspension of 1-(1-methylcyclopropylcarbonyl)-imidazole (13.5 g) in dry tetrahydrofuran (120 ml) was added dropwise whilst maintaining the temperature below -60° C. The mixture was stirred at -78° C. for 3 hours and the temperature was allowed to rise to room temperature. Hydrochloric acid (2M, 100 ml) was added cautiously and the mixture was extracted with ether (2×100 ml). The combined extracts were washed with hydrochloric acid (2M, 3×50 ml) and water (3×50 ml), dried (anhydrous sodium sulphate) and filtered. The filtrate was evaporated to dryness to give t-butyl 3-(1-methylcyclopropyl)-3-oxopropionate as an orange oil NMR (CDCl3) 0.65(m,2H), 1.1(m,2H), 1.25(s,3H), 1.4(s,9H), 3.2(s,2H). whilst maintaining the temperature below -70° C with stirring whilst maintaining the temperature below -70° C The mixture was stirred at -78° C. for 1 hour was added dropwise whilst maintaining the temperature below -60° C The mixture was stirred at -78° C. for 3 hours to rise to room temperature the mixture was extracted with ether (2×100 ml) The combined extracts were washed with hydrochloric acid (2M, 3×50 ml) and water (3×50 ml) dried (anhydrous sodium sulphate) filtered The filtrate was evaporated to dryness