1,3-diphenylpropan-1-ol

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

実験手順: To 6-2 (2.12 g, 10.0 mmol) in tetrahydrofuran (25 ml) under a nitrogen atmosphere was added ethyl 4-hydroxybenzoate (6-3) (1.66 g, 10.0 mmol) followed by triphenyl phosphine (3.15 g, 12.0 mmol). The mixture was cooled in an ice bath and diethyl azodicarboxylate (2.09 g, 12 mmol) was added. This mixture was stirred overnight at ambient temperature and the solvent was removed in vacuo. The residue was taken up in the water and the ether layer was separated, washed with sodium bicarbonate and water, dried, filtered and concentrated in vacuo to yield an oil. Chromatographic purification on silica gel gave 6-4 as a colorless oil. The mixture was cooled in an ice bath the solvent was removed in vacuo the ether layer was separated washed with sodium bicarbonate and water dried filtered concentrated in vacuo to yield an oil Chromatographic purification on silica gel

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

実験手順: β-Phenylpropiophenone (6-1) (7.5 g, 36.0 mmol) was suspended in ethanol (100 ml) and sodium borohydride (0.68 g, 18.0 mmol) was added under N2. The resulting solution was stirred at ambient temperature overnight. The ethanol was removed in vacuo and the residual oil-solid was taken up in ethyl acetate (100 ml) and water (30 ml). The ethyl acetate layer was removed, washed with water, dried, filtered and concentrated in vacuo to give 6-2 as a colorless oil. The ethanol was removed in vacuo The ethyl acetate layer was removed washed with water dried filtered concentrated in vacuo

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

実験手順: A solution of racemic 1,3-diphenyl-1-propanol (1.26 g; 5.94 mmol) was dissolved in 10 mL of acetone, and Jones reagent was added until persistence of the orange color. After stirring for 30 min, the reaction was quenched by adding 2 mL of 2-propanol. The solvent was decanted away from the precipitated solids, which were washed with ethyl acetate. The combined organic fractions were washed with 2×20 mL of water, dried and concentrated. The crude product was filtered through a plug of silica gel, eluting with 25% ethyl acetate/hexane, to obtain 1.07 g (86%) of 1,3-diphenylpropanone as a white crystalline solid, 1H NMR (360 Mhz; CDCl3): d 3.09 (t, 2H, J=8.1); 3.33 (t, 2H, J=8.1); 7.29 (m, 5H); 7.49 (m, 3H); 7.98 (m, 2H). the reaction was quenched by adding 2 mL of 2-propanol The solvent was decanted away from the precipitated solids, which were washed with ethyl acetate The combined organic fractions were washed with 2×20 mL of water dried concentrated The crude product was filtered through a plug of silica gel eluting with 25% ethyl acetate/hexane

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

実験手順: A solution of racemic 1,3-diphenyl-1-propanol (1.26 g; 5.94 mmol) was dissolved in 10 mL of acetone, and Jones reagent was added until persistence of the orange color. After stirring for 30 min, the reaction was quenched by adding 2 mL of 2-propanol. The solvent was decanted away from the precipitated solids, which were washed with ethyl acetate. The combined organic fractions were washed with 2×20 mL of water, dried and concentrated. The crude product was filtered through a plug of silica gel, eluting with 25% ethyl acetate/hexane, to obtain 1.07 g (86%) of 1,3-diphenylpropanone as a white crystalline solid, 1H NMR (360 Mhz; CDCl3): d 3.09 (t, 2H, J=8.1); 3.33 (t, 2H, J=8.1); 7.29 (m, 5H); 7.49 (m, 3H); 7.98 (m, 2H). the reaction was quenched by adding 2 mL of 2-propanol The solvent was decanted away from the precipitated solids, which were washed with ethyl acetate The combined organic fractions were washed with 2×20 mL of water dried concentrated The crude product was filtered through a plug of silica gel eluting with 25% ethyl acetate/hexane

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

実験手順: 0.301 g (1 mmol) of (3R)-4-(4-toluenesulfonyl)thiomorpholine-3-carboxylic acid, 0.318 g (1.5 mmol) of (1,3-diphenyl)-propanol, 0.088 g (0.33 mmol) of CAS, 0.227 g (1.2 mmol) of DCC and 0.04 g (0.33 mmol) of DMAP were dissolved in 15 mL of CH2Cl2. The mixture was stirred for 24 h at room temperature. The solid was filtrated and the solvent was evaporated. The residual was dissolved in a suitable amount of ethyl acetate (20 ml) and then the mixture was filtered to remove insoluble substance. The ethyl acetate was added to 60 ml and then the liquid was washed with 10% NaHCO3 solution, saturated NaCl solution and dried over Na2SO4. After the drying agent was removed and part of ethyl acetate was evaporated, the crude product was purified by flash column chromatography (eluent: ethyl acetate:cyclohexane=1:3) to obtain the product as a oil (0.15 g). 1H-NMR (400 MHz, CDCl3): δ 7.5040(d, 2H, J=8.32 Hz), 7.3751-7.0634 (m, 12H), 5.7186-5.6846 (m, 1H), 5.0645 (t, 1H, J=3.42 Hz), 4.0136-3.9800 (m, 1H), 3.4760-3.4052 (m, 1H), 3.1031-3.0773 (m, 2H), 2.8562-2.7914 (m, 1H), 2.6613-2.5414 (m, 2H), 2.4304-2.3855 (m, 1H), 2.3333 (s, 3H), 2.2283-2.2041 (m, 1H), 2.0565-2.0328 (m, 1H); MS (EI) m/z: 495.8, 449.8, 391.8, 339.8, 299.7, 255.7, 193.8, 154.8, 138.8, 116.9, 90.8, 64.9. The solid was filtrated the solvent was evaporated The residual was dissolved in a suitable amount of ethyl acetate (20 ml) the mixture was filtered to remove insoluble substance The ethyl acetate was added to 60 ml the liquid was washed with 10% NaHCO3 solution, saturated NaCl solution dried over Na2SO4 After the drying agent was removed part of ethyl acetate was evaporated the crude product was purified by flash column chromatography (eluent: ethyl acetate:cyclohexane=1:3)

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

実験手順: To 6-2 (2.12 g, 10.0 mmol) in tetrahydrofuran (25 ml) under a nitrogen atmosphere was added ethyl 4-hydroxybenzoate (6-3) (1.66 g, 10.0 mmol) followed by triphenyl phosphine (3.15 g, 12.0 mmol). The mixture was cooled in an ice bath and diethyl azodicarboxylate (2.09 g, 12 mmol) was added. This mixture was stirred overnight at ambient temperature and the solvent was removed in vacuo. The residue was taken up in the water and the ether layer was separated, washed with sodium bicarbonate and water, dried, filtered and concentrated in vacuo to yield an oil. Chromatographic purification on silica gel gave 6-4 as a colorless oil. The mixture was cooled in an ice bath the solvent was removed in vacuo the ether layer was separated washed with sodium bicarbonate and water dried filtered concentrated in vacuo to yield an oil Chromatographic purification on silica gel

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

実験手順: β-Phenylpropiophenone (6-1) (7.5 g, 36.0 mmol) was suspended in ethanol (100 ml) and sodium borohydride (0.68 g, 18.0 mmol) was added under N2. The resulting solution was stirred at ambient temperature overnight. The ethanol was removed in vacuo and the residual oil-solid was taken up in ethyl acetate (100 ml) and water (30 ml). The ethyl acetate layer was removed, washed with water, dried, filtered and concentrated in vacuo to give 6-2 as a colorless oil. The ethanol was removed in vacuo The ethyl acetate layer was removed washed with water dried filtered concentrated in vacuo

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

実験手順: β-Phenylpropiophenone (6-1) (7.5 g, 36.0 mmol) was suspended in ethanol (100 ml) and sodium borohydride (0.68 g, 18.0 mmol) was added under N2. The resulting solution was stirred at ambient temperature overnight. The ethanol was removed in vacuo and the residual oil-solid was taken up in ethyl acetate (100 ml) and water (30 ml). The ethyl acetate layer was removed, washed with water, dried, filtered and concentrated in vacuo to give 6-2 as a colorless oil. The ethanol was removed in vacuo The ethyl acetate layer was removed washed with water dried filtered concentrated in vacuo

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

実験手順: A solution of racemic 1,3-diphenyl-1-propanol (1.26 g; 5.94 mmol) was dissolved in 10 mL of acetone, and Jones reagent was added until persistence of the orange color. After stirring for 30 min, the reaction was quenched by adding 2 mL of 2-propanol. The solvent was decanted away from the precipitated solids, which were washed with ethyl acetate. The combined organic fractions were washed with 2 times 20 mL of water, dried and concentrated. The crude product was filtered through a plug of silica gel, eluting with 25% ethyl acetate/hexane, to obtain 1.07 g (86%) of 1,3-diphenylpropanone as a white crystalline solid, 1HNMR (360 MHz, CDCl3): d 3.09 (t, 2H, J=8.1); 3.33 (t, 2H, J=8.1); 7.29 (m, 5H); 7.49 (m, 3H); 7.98 (m, 2H). the reaction was quenched by adding 2 mL of 2-propanol The solvent was decanted away from the precipitated solids, which were washed with ethyl acetate The combined organic fractions were washed with 2 times 20 mL of water dried concentrated The crude product was filtered through a plug of silica gel eluting with 25% ethyl acetate/hexane

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

実験手順: A solution of racemic 1,3-diphenyl-1-propanol (1.26 g; 5.94 mmol) was dissolved in 10 mL of acetone, and Jones reagent was added until persistence of the orange color. After stirring for 30 min, the reaction was quenched by adding 2 mL of 2-propanol. The solvent was decanted away from the precipitated solids, which were washed with ethyl acetate. The combined organic fractions were washed with 2 times 20 mL of water, dried and concentrated. The crude product was filtered through a plug of silica gel, eluting with 25% ethyl acetate/hexane, to obtain 1.07 g (86%) of 1,3-diphenylpropanone as a white crystalline solid, 1HNMR (360 MHz, CDCl3): d 3.09 (t, 2H, J=8.1); 3.33 (t, 2H, J=8.1); 7.29 (m, 5H); 7.49 (m, 3H); 7.98 (m, 2H). the reaction was quenched by adding 2 mL of 2-propanol The solvent was decanted away from the precipitated solids, which were washed with ethyl acetate The combined organic fractions were washed with 2 times 20 mL of water dried concentrated The crude product was filtered through a plug of silica gel eluting with 25% ethyl acetate/hexane

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

実験手順: General procedure for conversion of racemic 1-substituted alkanols to optically active 1-substituted alkanols via prochiral ketones. Exemplified for (1 R)-1,3-diphenyl-1-propanol. A solution of racemic 1,3-diphenyl-1-propanol (1.26 g; 5.94 mmol) was dissolved in 10 mL of acetone, and Jones reagent was added until persistence of the orange color. After stirring for 30 min, the reaction was quenched by adding 2 mL of 2-propanol. The solvent was decanted away from the precipitated solids, which were washed with ethyl acetate. The combined organic fractions were washed with 2×20 mL of water, dried and concentrated. The crude product was filtered through a plug of silica gel, eluting with 25% ethyl acetate/hexane, to obtain 1.07 g (86%) of 1,3-diphenylpropanone as a white crystalline solid, 1H NMR (360 Mhz; CDCl3): d 3.09 (t, 2H, 1=8.1); 3.33 (t, 2H, 1=8.1); 7.29 (m, 5H); 7.49 (m, 3H); 7.98 (m, 2H). the reaction was quenched by adding 2 mL of 2-propanol The solvent was decanted away from the precipitated solids, which were washed with ethyl acetate The combined organic fractions were washed with 2×20 mL of water dried concentrated The crude product was filtered through a plug of silica gel eluting with 25% ethyl acetate/hexane

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

実験手順: A solution of racemic 1,3-diphenyl-1-propanol (1,26 g; 5.94 mmol) was dissolved in 10 mL of acetone, and Jones reagent was added until persistence of the orange color. After stirring for 30 min, the reaction was quenched by adding 2 mL of 2-propanol. The solvent was decanted away from the precipitated solids, which were washed with ethyl actetate. The combined organic fractions were washed with 2×20 mL of water, dried and concentrated. The crude product was filtered through a plug of silica gel, eluting with 25% ethyl acetate/hexane, to obtain 1.07 g (86%) of 1,3-diphenylpropanone as a white crystalline solid, 1H NMR (360 Mhz; CDCl3): δ 3.09 (t, 2H, J=8.1); 3.33 (t, 2H, J=8.1); 7.29 (m, 5H); 7.49 (m, 3H); 7.98 (m, 2H). the reaction was quenched by adding 2 mL of 2-propanol The solvent was decanted away from the precipitated solids, which were washed with ethyl actetate The combined organic fractions were washed with 2×20 mL of water dried concentrated The crude product was filtered through a plug of silica gel eluting with 25% ethyl acetate/hexane