hepta-1,6-dien-4-ol

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: n-Butyllithium, 129 mL (200 mmol), is added dropwise to a 0° C. solution of 1,6-heptadien-4-ol, 22.4 g (0.2 mol), in 200 mL of anhydrous tetrahydrofuran until the triphenylmethane indicator turned red. Carbon dioxide is then bubbled in for 30 minutes (lecture bottle carbon dioxide passed through drierite) and the light yellow solution is stirred for 30 minutes under a balloon of carbon dioxide. To this solution is added iodine, 101.4 g (0.4 mol), dissolved in ~200 mL of anhydrous tetrahydrofuran over 60 minutes. The mixture is allowed to warm to room temperature overnight, diluted with ethyl acetate, washed with 10% sodium bisulfite solution, saturated solution of sodium bicarbonate, brine, and dried (magnesium sulfate). The crude product is dissolved in 200 mL of methanol and 20 mL of water, cooled to 0° C. and 0.5 g of solid potassium carbonate is added. The mixture is vigorously stirred for six hours, filtered, concentrated, and partitioned between ethyl acetate and brine. After extracting the aqueous layer 2× with ethyl acetate, the combined organics are washed with brine and dried (magnesium sulfate). Flash chromatography (4:1 hexane-ethyl acetate) provides, after concentration in vacuo, 18 g of (R*,R*)-α-2-propenyloxiraneethanol. Carbon dioxide is then bubbled in for 30 minutes (lecture bottle carbon dioxide passed through drierite) To this solution is added iodine, 101.4 g (0.4 mol) dissolved in ~200 mL of anhydrous tetrahydrofuran over 60 minutes diluted with ethyl acetate washed with 10% sodium bisulfite solution, saturated solution of sodium bicarbonate, brine dried (magnesium sulfate) The crude product is dissolved in 200 mL of methanol 20 mL of water, cooled to 0° C. 0.5 g of solid potassium carbonate is added The mixture is vigorously stirred for six hours filtered concentrated partitioned between ethyl acetate and brine After extracting the aqueous layer 2× with ethyl acetate the combined organics are washed with brine dried (magnesium sulfate) Flash chromatography (4:1 hexane-ethyl acetate) provides after concentration in vacuo, 18 g of (R*,R*)-α-2-propenyloxiraneethanol

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

実験手順: 5-Bromopentanoyl chloride (3.0 g, 0.015 mol) was added dropwise to 1,6-heptadien-4-ol (1.5 g, 0.013 mol) and triethylamine (1.4 g, 0.014 mol) in DCM (25 cm3). The mixture was stirred for 2 h and washed with dilute hydrochloric acid (20%, 50 cm3), saturated aqueous potassium carbonate solution (50 cm3), water (50 cm3) then dried (MgSO4) and concentrated to a brown oil. The product was purified by dry flash chromatography, [silica gel, DCM] to yield a pale yellow oil (1.7 g, yield 48%). Purity >92% (GC). washed with dilute hydrochloric acid (20%, 50 cm3), saturated aqueous potassium carbonate solution (50 cm3), water (50 cm3) then dried (MgSO4) concentrated to a brown oil The product was purified by dry flash chromatography, [silica gel, DCM]

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

実験手順: 5-Bromopentanoyl chloride (3.0 g, 0.015 mol) was added dropwise to 1,6-heptadien-4-ol (1.5 g, 0.013 mol) and triethylamine (1.4 g, 0.014 mol) in DCM (25 cm3). The mixture was stirred for 2 h and washed with dilute hydrochloric acid (20%, 50 cm3), saturated aqueous potassium carbonate solution (50 cm3), water (50 cm3) then dried (MgSO4) and concentrated to a brown oil. The product was purified by dry flash chromatography, [silica gel, DCM] to yield a pale yellow oil (1.7 g, yield 48%). Purity >92% (GC). washed with dilute hydrochloric acid (20%, 50 cm3), saturated aqueous potassium carbonate solution (50 cm3), water (50 cm3) then dried (MgSO4) concentrated to a brown oil The product was purified by dry flash chromatography, [silica gel, DCM]

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

実験手順: 5-Bromopentanoyl chloride (3.0 g, 0.015 mol) was added dropwise to 1,6-heptadien-4-ol (1.5 g, 0.013 mol) and triethylamine (1.4 g, 0.014 mol) in DCM (25 cm3). The mixture was stirred for 2 h and washed with dilute hydrochloric acid (20%, 50 cm3), saturated aqueous potassium carbonate solution (50 cm3), water (50 cm3) then dried (MgSO4) and concentrated to a brown oil. The product was purified by dry flash chromatography [silica gel, DCM] to yield a pale yellow oil (1.7 g, yield 48%). Purity>92% (GC). washed with dilute hydrochloric acid (20%, 50 cm3), saturated aqueous potassium carbonate solution (50 cm3), water (50 cm3) then dried (MgSO4) concentrated to a brown oil The product was purified by dry flash chromatography [silica gel, DCM]

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

実験手順: n-Butyllithium, 129 mL (200 mmol), is added dropwise to a 0° C. solution of 1,6-heptadien-4-ol, 22.4 g (0.2 mol), in 200 mL of anhydrous tetrahydrofuran until the triphenylmethane indicator turned red. Carbon dioxide is then bubbled in for 30 minutes (lecture bottle carbon dioxide passed through drierite) and the light yellow solution is stirred for 30 minutes under a balloon of carbon dioxide. To this solution is added iodine, 101.4 g (0.4 mol), dissolved in ~200 mL of anhydrous tetrahydrofuran over 60 minutes. The mixture is allowed to warm to room temperature overnight, diluted with ethyl acetate, washed with 10% sodium bisulfite solution, saturated solution of sodium bicarbonate, brine, and dried (magnesium sulfate). The crude product is dissolved in 200 mL of methanol and 20 mL of water, cooled to 0° C. and 0.5 g of solid potassium carbonate is added. The mixture is vigorously stirred for six hours, filtered, concentrated, and partitioned between ethyl acetate and brine. After extracting the aqueous layer 2x with ethyl acetate, the combined organics are washed with brine and dried (magnesium sulfate). Flash chromatography (4:1 hexane-ethyl acetate) provides, after concentration in vacuo, 18 g of (R*,R*)-α-2-propenyloxiraneethanol. 200 MHz NMR (CDCl3) δ1.5-1.65 (m, 1H), 1.90 (dt, 1H, J=15, 4 Hz), 2.2 (m, 3H), 2.53 (m, 1H), 2.79 (m, 1H), 3.12 (m, 1H), 3.94 (m, 1H), 5.19 (m, 2H), 5.80 (m, 1H). Carbon dioxide is then bubbled in for 30 minutes (lecture bottle carbon dioxide passed through drierite) To this solution is added iodine, 101.4 g (0.4 mol) dissolved in ~200 mL of anhydrous tetrahydrofuran over 60 minutes diluted with ethyl acetate washed with 10% sodium bisulfite solution, saturated solution of sodium bicarbonate, brine dried (magnesium sulfate) The crude product is dissolved in 200 mL of methanol 20 mL of water, cooled to 0° C. 0.5 g of solid potassium carbonate is added The mixture is vigorously stirred for six hours filtered concentrated partitioned between ethyl acetate and brine After extracting the aqueous layer 2x with ethyl acetate the combined organics are washed with brine dried (magnesium sulfate) Flash chromatography (4:1 hexane-ethyl acetate) provides after concentration in vacuo, 18 g of (R*,R*)-α-2-propenyloxiraneethanol

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: There was supplied 1.35 g of imidazole manufactured by Wako Pure Chemical Industries, Ltd. to a 50 mL-Schlenk tube, and thereto, 10 mL of anhydrous N,N-dimethylformaide manufactured by Wako Pure Chemical Industries, Ltd., and 1.2 mL of 1,6-heptadien-4-ol manufactured by Aldrich Chemical Company were added. The obtained mixture was cooled down to 0° C. To the mixture, 1.93 mL of triisopropylsilyl chloride manufactured by Tokyo Chemical Industry Co., Ltd. was added, and the resultant mixture was stirred for 85 hours at a room temperature. Then, an excess amount of water was added thereto, thereby terminating the reaction. A product contained in the reaction mixture was extracted with hexane, and the obtained organic extract was dried over anhydrous sodium sulfate manufactured by Nacalai Tesque, Inc. The dried hexane solution was distilled in vacuo, thereby obtaining 1.1 g (yield: 46%) of 4-(triisopropylsiloxy)-1,6-heptadiene at 93° C. under 21 mmHg as clear colorless oil. were added was added terminating the reaction was extracted with hexane the obtained organic extract was dried over anhydrous sodium sulfate The dried hexane solution was distilled in vacuo

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: There were supplied 6.5 g of imidazole manufactured by Wako Pure Chemical Industries, Ltd. to a 100 mL-two neck flask, and thereto, 50 mL of anhydrous N,N-dimethylformaide manufactured by Wako Pure Chemical Industries, Ltd., and 5.78 mL of 1,6-heptadien-4-ol manufactured by Aldrich Chemical Company were added. The obtained mixture was cooled down to 0° C. To the mixture, 6.5 g of tert-butyldimethylsilyl chloride manufactured by Tokyo Chemical Industry Co., Ltd. were added, and the resultant mixture was stirred for 12 hours at a room temperature. Then, an excess amount of water was added thereto, thereby terminating the reaction. A product contained in the reaction mixture was extracted with hexane, and the obtained organic extract was dried over anhydrous sodium sulfate manufactured by Nacalai Tesque, Inc. The dried hexane solution was distilled in vacuo, thereby obtaining 2.88 g (yield: 30%) of 4-(tert-butyldimethylsiloxy)-1,6-heptadiene as clear colorless oil. were added were added terminating the reaction was extracted with hexane the obtained organic extract was dried over anhydrous sodium sulfate The dried hexane solution was distilled in vacuo

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Into a round-bottom flask, was placed a solution of hepta-1,6-dien-4-ol (2.00 g, 17.8 mmol, 1.00 equiv) and iodomethane (5.00 g, 35.2 mmol, 2.00 equiv) in tetrahydrofuran (30 mL). The solution was cooled to 0° C. and sodium hydride (1.00 g, 25.0 mmol, 1.50 equiv, 60% in mineral oil) was added to the reaction in portions. The resulting mixture was stirred overnight at room temperature, then carefully quenched with water (5 mL) and diluted with of ether (30 mL). The organics was washed with brine (2×20 mL), dried (Na2SO4), filtered and concentrated in vacuo to obtain the title compound as a colorless oil (2.00 g, 84%). Into a round-bottom flask, was placed carefully quenched with water (5 mL) diluted with of ether (30 mL) The organics was washed with brine (2×20 mL) dried (Na2SO4) filtered concentrated in vacuo

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Into a round-bottom flask, was placed a solution of hepta-1,6-dien-4-ol (2.00 g, 17.8 mmol, 1.00 equiv) and iodomethane (5.00 g, 35.2 mmol, 2.00 equiv) in tetrahydrofuran (30 mL). The solution was cooled to 0° C. and sodium hydride (1.00 g, 25.0 mmol, 1.50 equiv, 60% in mineral oil) was added to the reaction in portions. The resulting mixture was stirred overnight at room temperature, then carefully quenched with water (5 mL) and diluted with of ether (30 mL). The organics was washed with brine (2×20 mL), dried (Na2SO4), filtered and concentrated in vacuo to obtain the title compound as a colorless oil (2.00 g, 84%). Into a round-bottom flask, was placed carefully quenched with water (5 mL) diluted with of ether (30 mL) The organics was washed with brine (2×20 mL) dried (Na2SO4) filtered concentrated in vacuo

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

実験手順: n-Butyllithium, 129 mL (200 mmol), is added dropwise to a 0° C. solution of 1,6-heptadien-4-ol, 22.4 g (0.2 mol), in 200 mL of anhydrous tetrahydrofuran until the triphenylmethane indicator turned red. Carbon dioxide is then bubbled in for 30 minutes (lecture bottle carbon dioxide passed through drierite) and the light yellow solution is stirred for 30 minutes under a balloon of carbon dioxide. To this solution is added iodine, 101.4 g (0.4 mol), dissolved in ~200 mL of anhydrous tetrahydrofuran over 60 minutes. The mixture is allowed to warm to room temperature overnight, diluted with ethyl acetate, washed with 10% sodium bisulfite solution, saturated solution of sodium bicarbonate, brine, and dried (magnesium sulfate). The crude product is dissolved in 200 mL of methanol and 20 mL of water, cooled to 0° C. and 0.5 g of solid potassium carbonate is added. The mixture is vigorously stirred for six hours, filtered, concentrated, and partitioned between ethyl acetate and brine. After extracting the aqueous layer 2× with ethyl acetate, the combined organics are washed with brine and dried (magnesium sulfate). Flash chromatography (4:1 hexane-ethyl acetate) provides, after concentration in vacuo, 18 g of (R*,R*)-α-2-propenyloxiraneethanol. Carbon dioxide is then bubbled in for 30 minutes (lecture bottle carbon dioxide passed through drierite) To this solution is added iodine, 101.4 g (0.4 mol) dissolved in ~200 mL of anhydrous tetrahydrofuran over 60 minutes diluted with ethyl acetate washed with 10% sodium bisulfite solution, saturated solution of sodium bicarbonate, brine dried (magnesium sulfate) The crude product is dissolved in 200 mL of methanol 20 mL of water, cooled to 0° C. 0.5 g of solid potassium carbonate is added The mixture is vigorously stirred for six hours filtered concentrated partitioned between ethyl acetate and brine After extracting the aqueous layer 2× with ethyl acetate the combined organics are washed with brine dried (magnesium sulfate) Flash chromatography (4:1 hexane-ethyl acetate) provides after concentration in vacuo, 18 g of (R*,R*)-α-2-propenyloxiraneethanol