3-methoxycyclohex-2-en-1-one

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: The general procedure for the preparation of substrates using 3-methoxycyclohexenone (1.26 g, 10 mmol) and n-BuLi (20 mmol, 1.6 M in hexane) gave, after flash chromatography (4:1 hexanes:ethyl acetate) the title compound as a colorless liquid (1.48 g, 97%). Spectroscopic data were consistent with previously reported data for this compound.2 The general procedure for the preparation of substrates gave

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

実験手順: The general procedure for the preparation of substrates using 3-methoxycyclohexenone (1.26 g, 10 mmol) and n-BuLi (20 mmol, 1.6 M in hexane) gave, after flash chromatography (4:1 hexanes:ethyl acetate) the title compound as a colorless liquid (1.48 g, 97%). Spectroscopic data were consistent with previously reported data for this compound.2 The general procedure for the preparation of substrates gave

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

実験手順: The general procedure for the preparation of substrates using 3-methoxycyclohexenone (1.26 g, 10 mmol) and n-BuLi (20 mmol, 1.6 M in hexane) gave, after flash chromatography (4:1 hexanes:ethyl acetate) the title compound as a colorless liquid (1.48 g, 97%). Spectroscopic data were consistent with previously reported data for this compound.2 The general procedure for the preparation of substrates gave

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

実験手順: The general procedure for the preparation of substrates using 3-methoxycyclohexenone (1.26 g, 10 mmol) and n-BuLi (20 mmol, 1.6 M in hexane) gave, after flash chromatography (4:1 hexanes:ethyl acetate) the title compound as a colorless liquid (1.48 g, 97%). Spectroscopic data were consistent with previously reported data for this compound.2 The general procedure for the preparation of substrates gave

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

実験手順: 3-Methoxy-cyclohex-2-enone (7.8 g, 61.83 mmol) was dissolved in Et2O (100 mL) and titanium tetraisopropoxide (20.1 mL, 68.01 mmol) was added. To the resulting brown solution ethylmagnesium bromide solution (3M, 60 mL, 180 mmol) was added dropwise over 70 minutes. A precipitate formed over the course of the addition. After 2 hours at RT the now dark brown/black reaction mixture was carefully quenched with saturated aqueous NH4Cl. A dark gray precipitate formed and was filtered off over Celite. The aqueous layer was extracted twice with Et2O. The combined organic layers were washed with brine, dried (Na2SO4), filtered, and evaporated. The residue was taken up in Et2O (100 mL) and p-toluenesulfonic acid monohydrate (0.588 g, 3.091 mmol) was added. The resulting brown solution was stirred at RT over the weekend before being evaporated. The remaining brown oil was purified by SiO2 chromatography (330 g SiO2, hexanes/EtOAc 0 to 7% EtOAc) to give 2.5 g of spiro[2.5]octan-5-one as a light yellow liquid (32% yield). A precipitate formed over the course of the addition After 2 hours at RT the now dark brown/black reaction mixture was carefully quenched with saturated aqueous NH4Cl A dark gray precipitate formed was filtered off over Celite The aqueous layer was extracted twice with Et2O The combined organic layers were washed with brine dried (Na2SO4) filtered evaporated before being evaporated The remaining brown oil was purified by SiO2 chromatography (330 g SiO2, hexanes/EtOAc 0 to 7% EtOAc)

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

実験手順: n-Butyllithium (1.58M in hexane; 21 ml) was added at -78° under nitrogen to a stirred solution of diisopropylamine (4.6 ml) in dry THF (75 ml) and the solution was stirred at 0° for 30 min. The solution was cooled to -78° and added to a solution of 3-methoxy-2-cyclohexen-1 one (3.4 g) in dry THF (25 ml) at -78° under nitrogen with stirring. After stirring for 1 h at -78° and for 30 min. at 0° the solution was cooled to -78° and a solution of 4-(chloromethyl)-5-methyl-1-(triphenylmethyl)-1H-imidazole (10 g) in dry THF (100 ml) was added dropwise with stirring under nitrogen. The solution was stirred at -78° for 3 h and at 0° for 30 min., treated with 8% aqueous sodium bicarbonate (400 ml) and extracted with ethyl acetate (2×300 ml). The combined, dried organic extracts were evaporated to give an oil (ca. 13 g) which was purified by SPCC eluting with System A (967:30:3) to give the title compound (3.28 g), m.p. 145°-148°. The solution was cooled to -78° with stirring After stirring for 1 h at -78° and for 30 min. at 0° the solution was cooled to -78° with stirring under nitrogen The solution was stirred at -78° for 3 h and at 0° for 30 min. extracted with ethyl acetate (2×300 ml) dried organic extracts were evaporated

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

実験手順: Using the procedure of Example 2 with stirring of the reaction mixture for up to one day, 3-methoxycyclobut-2-en-1-one and 3-methoxycyclohex-2-en-1-one are prepared from 1,3-cyclobutanedione and 1,3-cyclohexanedione.

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

実験手順: Using the procedure of Example 2 with stirring of the reaction mixture for up to one day, 3-methoxycyclobut-2-en-1-one and 3-methoxycyclohex-2-en-1-one are prepared from 1,3-cyclobutanedione and 1,3-cyclohexanedione.

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: Butyllithium (143 ml of 1.4 molar solution in hexane) was added dropwise to a stirred solution of caprolactam (11.3 g) in dry tetrahydrofuran under nitrogen. After stirring for 50 minutes at 0°, 3-methoxy-2-cyclohexenone (12.6 g) in tetrahydrofuran was added. After a further 30 minutes the reaction was poured onto 5 M hydrochloric acid. The organic layer was separated and the aqueous layer was extracted with chloroform. The combined organic layers were dried over magnesium sulphate. Removal of the solvent under reduced pressure left 15 g of a yellow solid. The product was recrystallised from ethyl acetate affording 2.5 g of the title compound identical to that described in Example 17. The organic layer was separated the aqueous layer was extracted with chloroform The combined organic layers were dried over magnesium sulphate Removal of the solvent under reduced pressure left 15 g of a yellow solid The product was recrystallised from ethyl acetate affording 2.5 g of the title compound identical to

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

実験手順: A solution of hexahydro-1-phenylmethyl-2H-azepin-2-one (5.68 g) in dry THF was added at -10° C. to lithium diisopropylamide (0.032 mm) prepared from diisopropylamine (4.4 ml) and butyl lithium (22.9 ml of 1.4 M solution in hexane). The mixture was stirred for 30 minutes and then treated with a solution of 3-methoxy-2-cyclohexenone (2.53 g) in THF. After 5 hours at ambient temperature the mixture was poured onto ice-cold concentrated hydrochloric acid (100 ml). After vigorously stirring for 12 hours the solution was shaken with several portions of chloroform. The combined chloroform layers were evaporated to give an orange oil. This was refluxed with cupric bromide (8.95 g) and lithium bromide (1.74 g; 0.02 m) in acetonitrile for 1 hour. Removal of the solvent left a black oil that was triturated with excess 2 N sodium hydroxide solution. The filtrate, after removal of the orange precipitate, was extracted with methylene chloride. The organic layer was acidified (conc.HCl) and the white suspension shaken with several portions of chloroform and were evaporated to leave a dark red oil (1.2 g) that crystallised from ethyl acetate to give the title compound (0.35 g) m.p. 160°-166° C. After 5 hours at ambient temperature the mixture was poured onto ice-cold concentrated hydrochloric acid (100 ml) After vigorously stirring for 12 hours the solution The combined chloroform layers were evaporated to give an orange oil Removal of the solvent left a black oil that was triturated with excess 2 N sodium hydroxide solution The filtrate, after removal of the orange precipitate was extracted with methylene chloride the white suspension shaken with several portions of chloroform were evaporated