(1S)-1-phenylethanol

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

Procedure: A mixture of 2-fluorophenylacetic acid (5.45 g, 35.4 mmol), (S)-1-phenylethanol (5.62 g, 46.0 mmol), EDCI (8.82 g, 46.0 mmol) and DMAP (0.561 g, 4.60 mmol) in CH2Cl2 (100 mL) was stirred at room temperature for 12 hours. The solvent was then concentrated and the residue partitioned with H2O-ethyl acetate. The phases were separated and the aqueous layer back-extracted with ethyl acetate (2×). The combined organic phases were washed (H2O, brine), dried Na2SO4), filtered, and concentrated in vacuo. The residue was purified by silica gel chromatography (Biotage/0-20% ethyl acetate-hexane) to provide the title compound as a colorless oil (8.38 g, 92%). 1H NMR (400 MHz, CD3OD) δ 7.32-7.23 (m, 7H), 7.10-7.04 (m, 2), 5.85 (q, J=6.5 Hz, 1H), 3.71 (s, 2H), 1.48 (d, J=6.5 Hz, 3H). The solvent was then concentrated the residue partitioned with H2O-ethyl acetate The phases were separated the aqueous layer back-extracted with ethyl acetate (2×) The combined organic phases were washed (H2O, brine), dried Na2SO4), filtered concentrated in vacuo The residue was purified by silica gel chromatography (Biotage/0-20% ethyl acetate-hexane)

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

Procedure: To a mixture of α-bromophenylacetic acid (10.75 g, 0.050 mol), (S)-(−)-1-phenylethanol (7.94 g, 0.065 mol) and DMAP (0.61 g, 5.0 mmol) in dry dichloromethane (100 mL) was added solid EDCI (12.46 g, 0.065 mol) all at once. The resulting solution was stirred at room temperature under Ar for 18 hours and then it was diluted with ethyl acetate, washed (H2O×2, brine), dried (Na2SO4), filtered, and concentrated to give a pale yellow oil. Flash chromatography (SiO2/hexane-ethyl acetate, 4:1) of this oil provided the title compound (11.64 g, 73%) as a white solid. 1H NMR (400 MHz, CDCl3) δ 7.53-7.17 (m, 10H), 5.95 (q, J=6.6 Hz, 0.5H), 5.94 (q, J=6.6 Hz, 0.5H), 5.41 (s, 0.5H), 5.39 (s, 0.5H), 1.58 (d, J=6.6 Hz, 1.5H), 1.51 (d, J=6.6 Hz, 1.5H). washed (H2O×2, brine) dried (Na2SO4) filtered concentrated to give a pale yellow oil

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

Procedure: A mixture of 2-fluorophenylacetic acid (5.45 g, 35.4 mmol), (S)-1-phenylethanol (5.62 g, 46.0 mmol), EDCI (8.82 g, 46.0 mmol) and DMAP (0.561 g, 4.60 mmol) in CH2Cl2 (100 mL) was stirred at room temperature for 12 hours. The solvent was then concentrated and the residue partitioned with H2O-ethyl acetate. The phases were separated and the aqueous layer back-extracted with ethyl acetate (2×). The combined organic phases were washed (H2O, brine), dried (Na2SO4), filtered, and concentrated in vacuo. The residue was purified by silica gel chromatography (Biotage/0-20% ethyl acetate-hexane) to provide the title compound as a colorless oil (8.38 g, 92%). 1H NMR (400 MHz, CD3OD) δ 7.32-7.23 (m, 7H), 7.10-7.04 (m, 2), 5.85 (q, J=6.5 Hz, 1H), 3.71 (s, 2H), 1.48 (d, J=6.5 Hz, 3H). The solvent was then concentrated the residue partitioned with H2O-ethyl acetate The phases were separated the aqueous layer back-extracted with ethyl acetate (2×) The combined organic phases were washed (H2O, brine) dried (Na2SO4) filtered concentrated in vacuo The residue was purified by silica gel chromatography (Biotage/0-20% ethyl acetate-hexane)

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

Procedure: To a mixture of α-bromophenylacetic acid (10.75 g, 0.050 mol), (S)-(−)-1-phenylethanol (7.94 g, 0.065 mol) and DMAP (0.61 g, 5.0 mmol) in dry dichloromethane (100 mL) was added solid EDCI (12.46 g, 0.065 mol) all at once. The resulting solution was stirred at room temperature under Ar for 18 hours and then it was diluted with ethyl acetate, washed (H2O×2, brine), dried (Na2SO4), filtered, and concentrated to give a pale yellow oil. Flash chromatography (SiO2/hexane-ethyl acetate, 4:1) of this oil provided the title compound (11.64 g, 73%) as a white solid. 1H NMR (400 MHz, CDCl3) δ 7.53-7.17 (m, 10H), 5.95 (q, J=6.6 Hz, 0.5H), 5.94 (q, J=6.6 Hz, 0.5H), 5.41 (s, 0.5H), 5.39 (s, 0.5H), 1.58 (d, J=6.6 Hz, 1.5H), 1.51 (d, J=6.6 Hz, 1.5H). washed (H2O×2, brine) dried (Na2SO4) filtered concentrated to give a pale yellow oil

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

Procedure: A mixture of 2-fluorophenylacetic acid (5.45 g, 35.4 mmol), (S)-1-phenylethanol (5.62 g, 46.0 mmol), EDCI (8.82 g, 46.0 mmol) and DMAP (0.561 g, 4.60 mmol) in CH2Cl2 (100 mL) was stirred at room temperature for 12 hours. The solvent was then concentrated and the residue partitioned with H2O-ethyl acetate. The phases were separated and the aqueous layer back-extracted with ethyl acetate (2×). The combined organic phases were washed (H2O, brine), dried (Na2SO4), filtered, and concentrated in vacuo. The residue was purified by silica gel chromatography (BIOTAGE®/0-20% ethyl acetate-hexane) to provide the title compound as a colorless oil (8.38 g, 92%). 1H NMR (400 MHz, CD3OD) δ 7.32-7.23 (m, 7H), 7.10-7.04 (m, 2), 5.85 (q, J=6.5 Hz, 1H), 3.71 (s, 2H), 1.48 (d, J=6.5 Hz, 3H). The solvent was then concentrated the residue partitioned with H2O-ethyl acetate The phases were separated the aqueous layer back-extracted with ethyl acetate (2×) The combined organic phases were washed (H2O, brine) dried (Na2SO4) filtered concentrated in vacuo The residue was purified by silica gel chromatography (BIOTAGE®/0-20% ethyl acetate-hexane)

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

Procedure: To a mixture of α-bromophenylacetic acid (10.75 g, 0.050 mol), (S)-(−)-1-phenylethanol (7.94 g, 0.065 mol) and DMAP (0.61 g, 5.0 mmol) in dry dichloromethane (100 mL) was added solid EDCI (12.46 g, 0.065 mol) all at once. The resulting solution was stirred at room temperature under Ar for 18 hours and then it was diluted with ethyl acetate, washed (H2O×2, brine), dried (Na2SO4), filtered, and concentrated to give a pale yellow oil. Flash chromatography (SiO2/hexane-ethyl acetate, 4:1) of this oil provided the title compound (11.64 g, 73%) as a white solid. 1H NMR (400 MHz, CDCl3) δ 7.53-7.17 (m, 10H), 5.95 (q, J=6.6 Hz, 0.5H), 5.94 (q, J=6.6 Hz, 0.5H), 5.41 (s, 0.5H), 5.39 (s, 0.5H), 1.58 (d, J=6.6 Hz, 1.5H), 1.51 (d, J=6.6 Hz, 1.5H). washed (H2O×2, brine) dried (Na2SO4) filtered concentrated to give a pale yellow oil

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

Procedure: (R)-tert-Butyl 6-bromo-2-oxo-1-(1-phenylethyl)-1H-imidazo[4,5-b]pyridine-3(2H)-carboxylate. To a solution of tent-butyl 6-bromo-2-oxo-1H-imidazo[4,5-b]pyridine-3(2H)-carboxylate (1.6 g, 5.09 mmol), (S)-1-phenylethanol (0.75 g, 6.11 mmol) and triphenylphosphine (1.6 g, 6.11 mmol) in tetrahydrofuran (45 mL) was added diisopropyl azodicarboxylate (1.19 mL, 6.11 mmol). After stirring at room temperature for 1 h, the solvent was removed under reduced pressure. The crude product was purified by silica gel chromatography to afford the title compound (0.60 g, 28% yield). MS (ESI) m/z 418.2 [M+1]+. the solvent was removed under reduced pressure The crude product was purified by silica gel chromatography

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

Procedure: Washed cicer arietinum L (bengal grams) 50 g. were taken into a conical flask and allowed to soak in deionised water (400 ml) for a period of 24 hr. Acetophenone (0.500 g; 0.004 moles) I(a) was added to the soaked cicer arietinum L (bengal grams) in the above water, covered and allowed to shake for 24 hr at room temperature (28° C). Then the green grams were filtered off and washed with deionised water (3×100 ml). The combined filtrate was extracted with chloroform (3×500 ml). The chloroform layer was dried and the crude product obtained (80 mg.). Pure 1-phenyl-(1S)-ethan-1-ol II(a) was obtained after column chromatography with silica gel using chloroform as eluent. Washed cicer arietinum L (bengal grams) 50 g were taken into a conical flask to shake for 24 hr at room temperature (28° C) Then the green grams were filtered off washed with deionised water (3×100 ml) The combined filtrate was extracted with chloroform (3×500 ml) The chloroform layer was dried the crude product obtained (80 mg.)

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

Procedure: Washed phaseolus mungo L (black grams) 50 g. were taken into a conical flask and allowed to soak in deionised water (400 ml) for a period of 24 hr. Acetophenone (0.500 g; 0.004 moles) I(a) was added to the soaked phaseolus mungo L (black grams) in the above water, covered and allowed to shake for 24 hr at room temperature (28° C). Then the black grams were filtered off and washed with deionised water (3×100 ml). The combined filtrate was extracted with chloroform (3×500 ml). The chloroform layer was dried and the crude product obtained (0.1 g.). Pure 1-phenyl-(1S)-ethan-1-ol II(a) was obtained after column chromatography with silica gel using chloroform as eluent. Washed phaseolus mungo L (black grams) 50 g were taken into a conical flask to shake for 24 hr at room temperature (28° C) Then the black grams were filtered off washed with deionised water (3×100 ml) The combined filtrate was extracted with chloroform (3×500 ml) The chloroform layer was dried the crude product obtained (0.1 g.)

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

Procedure: Washed phaseolus aureus L (green grams) 500 g. were taken into a conical flask and allowed to soak in deionised water (4 L) for a period of 24 hr. Acetophenone (5 g; 0.0416 moles) I(a) was added to the soaked phaseolus aureus L (green grams) in the above water, covered and allowed to shake for 24 hr at room temperature (28° C). Then the green grams were filtered off and washed with deionised water (5×600 ml). The combined filtrate was extracted with chloroform (30×500 ml). The chloroform layer was dried and the crude product obtained (3.21 g.). Pure 1-phenyl-(1S)-ethan-1-ol II(a) was obtained after column chromatography with silica gel using chloroform as eluent. Washed phaseolus aureus L (green grams) 500 g were taken into a conical flask to shake for 24 hr at room temperature (28° C) Then the green grams were filtered off washed with deionised water (5×600 ml) The combined filtrate was extracted with chloroform (30×500 ml) The chloroform layer was dried the crude product obtained (3.21 g.)

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

Procedure: Washed phaseolus aureus L (green grams) 50 g. were taken into a conical flask and allowed to soak in deionised water (400 ml) for a period of 24 hr. Acetophenone (0.500 g; 0.004 moles) I(a) was added to the soaked phaseolus aureus L (green grams) in the above water, covered and allowed to shake for 24 hr at 15–20° C. Then the green grams were filtered off and washed with deionised water (3×100 ml). The combined filtrate was extracted with chloroform (3×500 ml). The chloroform layer was dried and the crude product obtained (360 mg). Pure 1-phenyl-(1S)-ethan-1-ol II(a) was obtained after column chromatography with silica gel using chloroform as eluent. Washed phaseolus aureus L (green grams) 50 g were taken into a conical flask to shake for 24 hr at 15–20° C Then the green grams were filtered off washed with deionised water (3×100 ml) The combined filtrate was extracted with chloroform (3×500 ml) The chloroform layer was dried the crude product obtained (360 mg)

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

Procedure: Continuing, using these immobilized beads as catalyst, 400 ml of distilled water equal to 20 times the weight of tartary buckwheat curd were added as reaction solvent. After making the temperature of the distilled water 35° C. using a constant-temperature shaking culturing vessel, 201 mg of ±-1-phenylethanol were added as substrate after which the conditions of the culturing vessel were set to 55 rpm and substrate conversion was performed for 8 days. (S)-1-phenylethanol was obtained at a conversion rate of 50%, optical purity of 95% e.e. and yield of 42% by going through the fourth and fifth steps under similar conditions as used with green pea protein. The yield of the formed acetophenone was 51% (102 mg).