4-phenylbutan-2-ol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a four-necked flask provided with a thermometer and a stirrer, 150 g (1 mol) of 4-phenyl-2-butanol (XXX-35), 500 ml of toluene and 200 ml of pyridine were charged. 122.4 g (1.2 mol) of anhydrous acetic acid and 1 g of 4-dimethylaminopyridine were further added thereto to react them for 4 hours, while temperature being maintained at 40°-50° C. After completion of the reaction, the reaction mixture was poured into 500 ml of 4N hydrochloric acid solution, extracted and fractionated, and then an organic layer was washed with 1N hydrochloric acid, water, 5% sodium bicarbonate solution and water in the order. The thus-obtained Organic layer was concentrated under a reduced pressure to obtain 189 g of 2-acetoxy-4-phenylbutane (XXIX-35) with yield of 98.5%. were charged to react them for 4 hours while temperature being maintained at 40°-50° C After completion of the reaction extracted an organic layer was washed with 1N hydrochloric acid, water, 5% sodium bicarbonate solution and water in the order The thus-obtained Organic layer was concentrated under a reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Into a four-necked flask provided with a thermometer and a stirrer, 150 g (1 mol) of 4-phenyl-2-butanol (XXX-35), 500 ml of toluene and 200 ml of pyridine were charged. 122.4 g (1.2 mol) of anhydrous acetic acid and 1 g of 4-dimethylaminopyridine were further added thereto to react them for 4 hours, while temperature being maintained at 40°-50° C. After completion of the reaction, the reaction mixture was poured into 500 ml of 4N hydrochloric acid solution, extracted and fractionated, and then an organic layer was washed with 1N hydrochloric acid, water, 5% sodium bicarbonate solution and water in the order. The thus-obtained Organic layer was concentrated under a reduced pressure to obtain 189 g of 2-acetoxy-4-phenylbutane (XXIX-35) with yield of 98.5%. were charged to react them for 4 hours while temperature being maintained at 40°-50° C After completion of the reaction extracted an organic layer was washed with 1N hydrochloric acid, water, 5% sodium bicarbonate solution and water in the order The thus-obtained Organic layer was concentrated under a reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: This half-ester R-3c (250 mg; 1.0 mmol) was dissolved in methanol (2 mL) and treated with potassium carbonate (276 mg; 2.0 mmol; 2 equiv.) and stirred overnight to completely consume 3c (tlc analysis). The reaction mixture was diluted with water (25 mL) and extracted with ether (3×10 mL). The combined extracts were dried (MgSO4) and concentrated to afford 118 mg (79%) of R-1c. All achiral properties of 1c are as reported above. The absolute configuration of 1c was not exhaustively proven, but was presumed to be R-(-) by analogy with the enzymatic results of 1a and 1b. 1H nmr analysis of the MTPA ester using an analogous procedure to that of Dale et al., J. Org. Chem., 1969, 34, 2543, indicated 54% ee for R-1c. [α]D20 -8.2° (c. 1.19, CH3OH). to completely consume 3c (tlc analysis) The reaction mixture was diluted with water (25 mL) extracted with ether (3×10 mL) The combined extracts were dried (MgSO4) concentrated to afford 118 mg (79%) of R-1c

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Benzylacetone (7.5 mL, 50 mmol) was dissolved in ethanol (50 mL) and cooled to 0° C. Sodium borohydride (1.89 g, 50 mmol, 1 equiv.) was added. The mixture was stirred and allowed to warm to room temperature overnight. All of the starting material was gone by tlc analysis, so the mixture was poured into water (50 mL) and ether (50 mL). The layers were separated and the aqueous layer was extracted with ether (2×25 mL). The organic layers were combined and concentrated. The resulting aqueous residue was poured into ether (50 mL). The organic layer was removed, dried (MgSO4), and concentrated to provide 1c (6.86 g; 91%). 1H nmr (300 MHz, CDCl3): 7.38-7.15 (5H, m); 3.85 (1H, m(6), J=6.17 Hz); 2.82-2.61 (2H, m); 1.79 (2H, q, J=7.12 Hz); 1.421 (1H, s); 1.236 (3H, d, J=6.09 Hz). IR (neat film, cm-1): 3250 (b); 2900 (b). EIMS (m/e): 150 (M+). to warm to room temperature overnight The layers were separated the aqueous layer was extracted with ether (2×25 mL) concentrated The resulting aqueous residue was poured into ether (50 mL) The organic layer was removed dried (MgSO4) concentrated

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Benzylacetone (7.5 mL, 50 mmol) was dissolved in ethanol (50 mL) and cooled to 0° C. Sodium borohydride (1.89 g, 50 mmol, 1 equiv.) was added. The mixture was stirred and allowed to warm to room temperature overnight. All of the starting material was gone by tlc analysis, so the mixture was poured into water (50 mL) and ether (50 mL). The layers were separated and the aqueous layer was extracted with ether (2×25 mL). The organic layers were combined and concentrated. The resulting aqueous residue was poured into ether (50 mL). The organic layer was removed, dried (MgSO4), and concentrated to provide 1c (6.86 g; 91%). 1H nmr (300 MHz, CDCl3): 7.38-7.15 (5H, m); 3.85 (1H, m(6), J=6.17 Hz); 2.82-2.61 (2H, m); 1.79 (2H, q, J=7.12 Hz); 1.421 (1H, s); 1.236 (3H, d, J=6.09 Hz). IR (neat film, cm-1): 3250 (b); 2900 (b). EIMS (m/e): 150 (M+). to warm to room temperature overnight The layers were separated the aqueous layer was extracted with ether (2×25 mL) concentrated The resulting aqueous residue was poured into ether (50 mL) The organic layer was removed dried (MgSO4) concentrated

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: RuClCp* (cod) (3.8 mg, 0.01 mmol), KOH (0.04 mmol), 2,2′-bipyridyl (3.1 mg, 0.02 mmol) and benzalacetone (730.95 mg, 5.0 mmol) were dissolved into 10 ml of 2-propanol, and deaerated by argon substitution, after which the total amount of the resulting mixture was transferred into a 100-milliliter metallic autoclave. Hydrogen was then charged to a predetermined pressure (50 atm), and the reaction was started at room temperature (28° C.). After the reaction solution was stirred for 3 hours, the reaction pressure was brought back to atmospheric pressure, and the reaction products, 4-phenyl-2-butanone (yield 19.8%) and 4-phenyl-2-butanol (yield 80.2%), were identified and determined by TLC monitor (silica gel: n-hexane/ethyl acetate=4/1) and gas chromatography of the reaction solution. was started at room temperature (28° C.) the reaction pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-(1-Hydroxyethyl)pyridine (76.8 mg, 0.624 mmol) was oxidized in the same manner as that described in Example 8, (a) (except that Nor-AZADO was used at 3 mol %, and the reaction was performed at room temperature) to obtain the objective compound (66.0 mg; yield, 87.4%). The spectrum data were found to be the same as those obtained in Example 6, (h). was performed at room temperature to obtain the objective compound (66.0 mg; yield, 87.4%)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of 4-phenylbutan-2-ol (97.7 mg, 0.651 mmol), Nor-AZADO (0.90 mg, 6.51 μmol, 1 mol %) and acetic acid (37 μl, 0.651 mmol) in dichloromethane (0.65 ml) was added with DIAD (128 μl, 0.651 mmol, 1 equivalent), and the mixture was stirred for 8 hours under reflux by heating. The reaction mixture was added with saturated aqueous sodium carbonate (2 ml), and the mixture was extracted with dichloromethane. The organic layer was dried over sodium sulfate, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain the objective compound (95.1 mg; yield, 99%). The spectrum data were found to be the same as those obtained in Example 5, (b). under reflux by heating the mixture was extracted with dichloromethane The organic layer was dried over sodium sulfate concentrated under reduced pressure The residue was purified by silica gel column chromatography to obtain the objective compound (95.1 mg; yield, 99%)