dec-9-yn-1-ol

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

実験手順: A solution of 88.7 g (392.5 mmol) of the trimethylsilyl ether of 9-decyn-1-ol (from Example 1) in 100 ml of THF is cooled to -70°. To this is added, dropwise, 245.3 ml (392.5 mmol) of n-butyllithium (1.6 in hexane), after which the mixture is warmed to -40° and poured into the hexenyldicyclohexylborane solution from above. This mixture is stirred at 0° for 30 min. and then cooled to -35°. Tri-n-butyltin chloride (128 g, 124 ml) is added, and the mixture is allowed to warm to ~20° and stirred for 1.5 hours. Acetic acid (186 ml) is then added dropwise and the mixture is stirred overnight at 50°. 2 N sulfuric acid (80 ml) is then added. After 30 min., the mixture is cooled and 392.5 ml of 6 N sodium hydroxide is added, followed by the addition, in portions, of 94.2 ml of 30% hydrogen peroxide at ~30°. The reaction mixture is worked up by dilution with water and extraction with hexane. The hexane layer is washed with concentrated aqueous sodium bisulfite and with brine, dried, and stripped of solvent and cyclohexanol under vacuum (0.05 mm). The crude product is chromatographed on a column of silica gel, eluting with hexane, then 10% ether/hexane and finally 20% ether/hexane. Recrystallization from 400 ml of hexane (3X) at -60° gives (9Z, 11E)-9,11-hexadecadien-1-ol containing about 8% of the E, E isomer. This product is further purified by dissolving it in 150 ml THF, adding a solution of 3 g of tetracyanoethylene in 80 ml of THF and stirring the mixture overnight at room temperature. The THF is stripped under vacuum and the product is purified by chromatography on a column of silica gel, eluting with hexane, then 10% ether/hexane and finally 20% ether/hexane. Low temperature recrystallization (-60°) from hexane (3X 500 ml) yields the product (9Z, 11E)-9,11-hexadecadien-1-ol. To this is added cooled to -35° to warm to ~20° stirred for 1.5 hours the mixture is stirred overnight at 50° After 30 min. the mixture is cooled The reaction mixture is worked up by dilution with water and extraction with hexane The hexane layer is washed with concentrated aqueous sodium bisulfite and with brine dried The crude product is chromatographed on a column of silica gel eluting with hexane Recrystallization from 400 ml of hexane (3X) at -60°

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

実験手順: To a flame-dried round-bottomed flask was added 9-decyn-1-ol (1 equiv, 32.4 mmol, 5.00 g), dihydropyran (1.5 equiv, 48.6 mmol, 4.09 g, 4.5 mL), CH2Cl2 (50 mL), and PPTS (0.1 equiv, 3.24 mmol, 800 mg). The reaction was stirred for 16 h at rt and quenched with sat. aq. NaHCO3 (40 mL). The layers were separated and the aqueous layer was extracted with CH2Cl2 (2×20 mL). The combined organic layers were washed with H2O (30 mL), dried with Na2SO4, concentrated in vacuo, and purified by flash column chromatography (5% EtOAc/Hex) to afford 9-Decyn-1-ol tetrahydropyranyl ether (7.55 g, 31.7 mmol, 98%). TLC Rf=0.30 (5% EtOAc/Hex); 1HNMR (600 MHz): δ 4.55-4.62 (1H), 3.83-3.91 (m, 1H), 3.70-3.78 (m, 1H), 3.48-3.55 (m, 1H), 3.36-3.43 (m, 1H), 2.19 (td, 2H, J1=7.1 Hz, J2=2.6 Hz), 1.95 (t, 1H, J=2.6), 1.80-1.89 (1H), 1.69-1.76 (1H), 1.50-1.63 (8H), 1.28-1.44 (8H); 13CNMR (150 MHz): δ 98.8, 84.7, 68.1, 67.6, 62.3, 30.8, 29.7, 29.3, 29.0, 28.7, 28.5, 26.2, 25.5, 19.7, 18.4. quenched with sat. aq. NaHCO3 (40 mL) The layers were separated the aqueous layer was extracted with CH2Cl2 (2×20 mL) The combined organic layers were washed with H2O (30 mL) dried with Na2SO4 concentrated in vacuo purified by flash column chromatography (5% EtOAc/Hex)