1-(2-methylphenyl)ethanol

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

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

Procedure: A solution of triphenylphosphine(5.48 g) in dry THF (35 mL) is treated with diisopropyl azodicarboxylate (4.23 g) at 0-5° C. and stirred for 15 minutes. The suspension is treated dropwise with a solution of methyl 4-benzyloxy-2-hydroxybenzoate (2.7 g) and 1-o-tolylethanol (1.42 g) in dry THF (35 mL) during 25 minutes at 0-5° C. and then stirred at 0-5° C. for 1 hour and at 25° C. for 24 hours. The mixture is evaporated and the residual gum purified by flash chromatography on silica, eluting with dichloromethane. Fractions homogeneous in the required product are combined and evaporated to yield methyl 4-benzyloxy-2-(1-o-tolyiethoxy)benzoate as a colourless oil (2.83 g, 72%). 1H NMR (CDCl3) 1.6(3H,d), 2.4(3H,s), 3.9(3H,s), 4.9(2H,s), 5.5(1H,q), 6.3(1H,s), 6.5(1H,d), 7.1-7.6(9H,m), 7.8(1H,d). stirred at 0-5° C. for 1 hour and at 25° C. for 24 hours The mixture is evaporated the residual gum purified by flash chromatography on silica eluting with dichloromethane evaporated

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

Procedure: 400 g of dichloroethane and 110 g (1.2 mol) of toluene were introduced initially together with 63 g (0.47 mol) of AlCl3 in the presence of 3 g (10-2 mol) of titanium tetraisopropylate or in the absence of titanium alcoholate. 44 g (1 mol) of ethylene oxide were added in the course of 1.5 h at the temperature stated in Table 3. After hydrolysis the reaction mixture was concentrated and analyzed by gas chromatography. The yields of 2-tolylethanol, obtained as a mixture of isomers, based on converted toluene, are shown in the following table: After hydrolysis the reaction mixture was concentrated

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

Procedure: A solution of triphenylphosphine(5.48 g) in dry THF (35 mL) is treated with diisopropyl azodicarboxylate (4.23 g) at 0-5° C. and stirred for 15 minutes. The suspension is treated dropwise with a solution of methyl 4-benzyloxy-2-hydroxybenzoate (2.7 g) and 1-o-tolylethanol (1.42 g) in dry THF (35 mL) during 25 minutes at 0-5° C. and then stirred at 0-5° C. for 1 hour and at 25° C. for 24 hours. The mixture is evaporated and the residual gum purified by flash chromatography on silica, eluting with dichloromethane. Fractions homogeneous in the required product are combined and evaporated to yield methyl 4-benzyloxy-2-(1-o-tolyiethoxy)benzoate as a colourless oil (2.83 g, 72%). 1H NMR (CDCl3) 1.6(3H,d), 2.4(3H,s), 3.9(3H,s), 4.9(2H,s), 5.5(1H,q), 6.3(1H,s), 6.5(1H,d), 7.1-7.6(9H,m), 7.8(1H,d). stirred at 0-5° C. for 1 hour and at 25° C. for 24 hours The mixture is evaporated the residual gum purified by flash chromatography on silica eluting with dichloromethane evaporated

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

Procedure: A solution of triphenylphosphine(5.48 g) in dry THF (35 mL) is treated with diisopropyl azodicarboxylate (4.23 g) at 0-5° C. and stirred for 15 minutes. The suspension is treated dropwise with a solution of methyl 4-benzyloxy-2-hydroxybenzoate (2.7 g) and 1-o-tolylethanol (1.42 g) in dry THF (35 mL) during 25 minutes at 0-5° C. and then stirred at 0-5° C. for 1 hour and at 25° C. for 24 hours. The mixture is evaporated and the residual gum purified by flash chromatography on silica, eluting with dichloromethane. Fractions homogeneous in the required product are combined and evaporated to yield methyl 4-benzyloxy-2-(1-o-tolyiethoxy)benzoate as a colourless oil (2.83 g, 72%). 1H NMR (CDCl3) 1.6(3H,d), 2.4(3H,s), 3.9(3H,s), 4.9(2H,s), 5.5(1H,q), 6.3(1H,s), 6.5(1H,d), 7.1-7.6(9H,m), 7.8(1H,d). stirred at 0-5° C. for 1 hour and at 25° C. for 24 hours The mixture is evaporated the residual gum purified by flash chromatography on silica eluting with dichloromethane evaporated

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

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

Procedure: In a similar manner as described for example B31, 1.50 g of methyl 5-[6-({[tert-butyl(dimethyl)silyl]oxy}methyl)-1H-imidazo[4,5-c]pyridin-1-yl]-3-hydroxythiophene-2-carboxylate, 0.63 g of 1-(2-methylphenyl)ethanol, 2.4 g of triphenylphosphine (polymer bound, ˜3 mmol/g) and 1.66 g of di-tert-butyl azodicarboxylate in 40 ml anhydrous dichloromethane yield the title compound.

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

Procedure: Sodium borohydride (564 mg) was added to a solution of 2-methylacetophenone (1 g) in a mixture of THF (8 mL) with methanol (32 mL), and the reaction solution was stirred at room temperature for 20 minutes. Water and ethyl acetate were added to the reaction solution and the organic layer was partitioned. The resulting organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (heptane-ethyl acetate system) to obtain 911 mg of the title compound. The physical properties of the compound are as follows. the organic layer was partitioned The resulting organic layer was dried over magnesium sulfate the solvent was evaporated under reduced pressure The residue was purified by silica gel column chromatography (heptane-ethyl acetate system)

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

Procedure: Sodium borohydride (564 mg) was added to a solution of 2-methylacetophenone (1 g) in a mixture of THF (8 mL) with methanol (32 mL), and the reaction solution was stirred at room temperature for 20 minutes. Water and ethyl acetate were added to the reaction solution and the organic layer was partitioned. The resulting organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (heptane-ethyl acetate system) to obtain 911 mg of the title compound. The physical properties of the compound are as follows. the organic layer was partitioned The resulting organic layer was dried over magnesium sulfate the solvent was evaporated under reduced pressure The residue was purified by silica gel column chromatography (heptane-ethyl acetate system)

Conditions: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Dichloro(p-cymene)ruthenium(II) dimer (1.2 mg, 2 μmol, 0.5 mol %) and a chiral ligand (M=Fe, R=i-Pr, Ar=C6H5—, 2.6 μmol, 0.65 mol %) were dissolved in toluene (3 mL) under nitrogen atmosphere, and then heated and stirred for 2 h at 120° C. After the mixture was cooled to room temperature, o-methylacetophenone (0.4 mmol), toluene (2 mL) and an aqueous solution of potassium hydroxide (0.4 mL, 0.2 M) were added thereto. Thereafter, the reaction system was placed in an autoclave, and stirred for 24 h under H2 (10 atm) at 25° C. The solvent was removed under reduced pressure, and the resultants were separated by column chromatography (silica gel column; eluent:ethyl acetate/petroleum ether=1/5). Accordingly, pure 1-(o-methylphenyl)ethanol was obtained and the ee value (ee=98%) was measured by GC analysis. heated After the mixture was cooled to room temperature stirred for 24 h under H2 (10 atm) at 25° C The solvent was removed under reduced pressure the resultants were separated by column chromatography (silica gel column; eluent:ethyl acetate/petroleum ether=1/5)

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

Procedure: In a dry flask under nitrogen atomosphere was suspended 3.25 g (0.086 mol) lithium aluminum hydride and 250 ml of dry diethyl ether. The suspension was cooled in an ice/water bath, then 24.5 g (0.184 mol) of 2-methylacetophenone was added dropwise. After 12 hours the excess hydride was decomposed with 100 ml of ethyl acetate. The reaction mixture was washed with ammonium chloride solution and water. The organic layer was dried (MgSO4) and concentrated under reduced pressure to give 25.0 g of a clear oil. In a dry flask under nitrogen atomosphere was suspended The suspension was cooled in an ice/water bath The reaction mixture was washed with ammonium chloride solution and water The organic layer was dried (MgSO4) concentrated under reduced pressure

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

Procedure: Sodium borohydride (564 mg) was added to a solution of 2-methylacetophenone (1 g) in a mixture of THF (8 mL) with methanol (32 mL), and the reaction solution was stirred at room temperature for 20 minutes. Water and ethyl acetate were added to the reaction solution and the organic layer was partitioned. The resulting organic layer was dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (heptane-ethyl acetate system) to obtain 911 mg of the title compound. The physical properties of the compound are as follows. the organic layer was partitioned The resulting organic layer was dried over magnesium sulfate the solvent was evaporated under reduced pressure The residue was purified by silica gel column chromatography (heptane-ethyl acetate system)