3,5,5,8,8-pentamethyl-6,7-dihydronaphthalene-2-carbaldehyde

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:

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: A 0° C., 3M tetrahydrofuran solution of 350 mg (1.62 mmol) of 2-formyl-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-naphthalene and 541 mg (1.78 mmol) of diethyl 2-fluoro-4-carbomethoxybenzylphosphonate was treated with 84 mg (2.10 mmol, 60% wt. in mineral oil) NaH in 10 mg portions over 10 minutes. The reaction mixture was stirred at room temperature for 2 hours before diluting with ethyl acetate and washing with brine. The organic extracts were dried over magnesium sulfate, concentrated in vacuo and triturated with methanol to provide 330 mg (54%) Methyl 2-fluoro-4-[(E)-2-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-naphthalen-2-yl)vinyl]benzoate. washing with brine The organic extracts were dried over magnesium sulfate concentrated in vacuo triturated with methanol

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

実験手順: To a solution of 18.7 g (82.3 mmol) of 2-cyano-3-methyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene in 280 mL of dichloromethane, cooled at −78°, was added 123 mL (123 mmol) of diisobutyl aluminum hydride (1.0 M in toluene). The reaction mixture was stirred and allowed to gradually warm to room temperature. After 16 hours, the reaction mixture was treated with 30 mL of acetic acid added dropwise, followed by 150 mL of water. The organic layer was separated, diluted with 200 mL of hexane, washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by flash chromatography (gradient elution 5-10% ethyl acetate/hexane) on silica gel to afford 11.8 g (63%) of 2-formyl-3-methyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene. added dropwise The organic layer was separated diluted with 200 mL of hexane washed with brine dried over sodium sulfate concentrated under reduced pressure The residue was purified by flash chromatography (gradient elution 5-10% ethyl acetate/hexane) on silica gel

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

実験手順: 22.2 mL (35.2 mmol) of n-butyl lithium (1.6 M in hexanes) was added. After 1 hours, a solution of 3.95 mL (35.5 mmol) of N-formylpiperidine was added to a solution of 5 g (17.8 mmol) of 2-bromo-3-methyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene in 50 mL of tetrahydrofuran, cooled in a dry ice/acetone bath. After 30 minutes 30 mL of saturated aqueous ammonium chloride was added to the reaction mixture. The reaction mixture was warmed to room temperature and extracted with ethyl acetate. The organic phase was separated, washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel with gradient elution (hexane-10% ethyl acetate/hexane) to provide 3.5 g (85%) of 2-formyl-3-methyl-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalene (m.p.: 82.4-84.1° C.). cooled in a dry ice/acetone bath extracted with ethyl acetate The organic phase was separated washed with brine dried over sodium sulfate concentrated under reduced pressure The residue was purified by flash chromatography on silica gel with gradient elution (hexane-10% ethyl acetate/hexane)