2-[(4-methoxyphenyl)methyl]phenol

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: To a solution of 2-(4-methoxybenzyl)phenol (46 mg) and 2,3,4,6-tetra-O-acetyl-1-O-trichloroacetoimidoyl-α-D-glucopyranose (0.13 g) in dichloromethane (2 mL) was added boron trifluoride diethyl ether complex (0.033 mL), and the mixture was stirred at room temperature for 1 hour. The reaction mixture was purified by column chromatography on aminopropyl silica gel (eluent: dichloromethane) to give 2-(4-methoxybenzyl)phenyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside (0.11 g). The reaction mixture was purified by column chromatography on aminopropyl silica gel (eluent: dichloromethane)

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

実験手順: To a solution of 2-(4-methoxybenzyl)phenol (46 mg) and 2,3,4,6-tetra-O-acetyl-1-O-trichloroacetoimidoyl-α-D-glucopyranose (0.13 g) in dichloromethane (2 mL) was added boron trifluoride diethyl ether complex (0.033 mL), and the mixture was stirred at room temperature for 1 hour. The reaction mixture was purified by column chromatography on aminopropyl silica gel (eluent: dichloromethane) to give 2-(4-methoxybenzyl)phenyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside (0.11 g). The reaction mixture was purified by column chromatography on aminopropyl silica gel (eluent: dichloromethane)

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

実験手順: To a solution of 2-(4-methoxybenzyl)phenol (46 mg) and 2,3,4,6-tetra-O-acetyl-1-O-trichloroacetoimidoyl-α-D-glucopyranose (0.13 g) in dichloromethane (2 mL) was added boron trifluoride diethyl ether complex (0.033 mL), and the mixture was stirred at room temperature for 1 hour. The reaction mixture was purified by column chromatography on aminopropyl silica gel (eluent: dichloromethane) to give 2-(4-methoxybenzyl)phenyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside (0.11 g). The reaction mixture was purified by column chromatography on aminopropyl silica gel (eluent: dichloromethane)

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

実験手順: (6R,7S,8S)-6,7,8-Tris-benzyloxy-4-oxaspiro[2.5]octan-5-ol (prepared according to an analogous procedure as described in J. Org. Chem. 2002, 67, 3733; Helv. Chim, Acta 1990, 73, 1329; Tetrahedron Lett. 1998, 39, 2021) (220 mg, 0.49 mmol) 2-(4-methoxybenzyl)-phenol (105 mg, 0.49 mmol) and triphenyl phosphine (155 mg, 0.59 mmol) were mixed under argon atmosphere followed by the addition of dry THF. The contents were cooled to 0° C. and DIAD (0.12 ml, 0.59 mmol) was added drop wise. The reaction mixture was refluxed for 12 hours and quenched with 1N dil. HCl (2 mL) and extracted with ethyl acetate (10×3 mL). Organic layer was washed with brine, dried over Na2SO4, concentrated under reduced pressure to give the crude product which was purified by flash column chromatography using 1:4 (Ethyl acetate:Hexane) as eluent to yield 200 mg of 5R,6R,7S,8S)-6,7,8-tris-benzyloxy-5-[2-(4-methoxy-benzyl)-phenoxy]-4-oxa-spiro[2.5]octane. The reaction mixture was refluxed for 12 hours quenched with 1N dil. HCl (2 mL) extracted with ethyl acetate (10×3 mL) Organic layer was washed with brine dried over Na2SO4 concentrated under reduced pressure to give the crude product which was purified by flash column chromatography

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

実験手順: 0.78 g of (2-hydroxyphenyl)(4-methoxyphenyl)methanone is dissolved in acetonitrile and cooled to 0° C. 2 ml of TMSCl are added dropwise to the mixture, and then 1 g of sodium cyanoborohydride is added. The mixture is stirred at room temperature for 3 h. The reaction solution is diluted with dichloromethane and filtered through Celite. filtered through Celite

反応条件: temp:180.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a 100-ml, four-necked flask equipped with a mechanical stirrer, a reflux condenser and a thermometer were placed 21.6 g (0.1 mole) of the 2-(4-methoxybenzylidene)cyclohexanone produced in Example 8 and 51.7 g (0.3 mole) of diethyl maleate in this order. The flask inside was purged with nitrogen. Thereto was added 2.2 g (10 wt. %, 1.0 mmole as palladium) of 5% palladium carbon (a product of Wako Pure Chemical Industries, Ltd.). The mixture was stirred at 180° C. for 6 hours and cooled to room temperature. 200 ml of toluene was added to the system. Filtration was conducted to remove the palladium carbon. The filtrate was extracted with 150 ml of a 7% aqueous sodium hydroxide solution, and this operation was repeated twice. The aqueous layer was washed with 50 ml of toluene. To the resulting aqueous layer was added 35% hydrochloric acid until the aqueous layer became acidic, after which the aqueous layer was extracted with 150 ml of ethyl acetate. The ethyl acetate layer was washed with water and a saturated aqueous sodium chloride solution in this order. The ethyl acetate layer was dried over anhydrous sodium sulfate and then subjected to vacuum distillation to remove ethyl acetate, to obtain 13.3 g of light yellow crystals. Yield: 62% The purity of the intended product in the crystals was 97% as measured by high performance liquid chromatography. In a 100-ml, four-necked flask equipped with a mechanical stirrer, a reflux condenser The flask inside was purged with nitrogen cooled to room temperature Filtration to remove the palladium carbon The filtrate was extracted with 150 ml of a 7% aqueous sodium hydroxide solution The aqueous layer was washed with 50 ml of toluene To the resulting aqueous layer was added 35% hydrochloric acid until the aqueous layer after which the aqueous layer was extracted with 150 ml of ethyl acetate The ethyl acetate layer was washed with water The ethyl acetate layer was dried over anhydrous sodium sulfate subjected to vacuum distillation to remove ethyl acetate