methyl 2-amino-3-(4-chlorophenyl)propanoate

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

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

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

Procedure: Methyl ester 1-1 (394 mg, 1.58 mmol) was dissolved in methylene chloride (4.0 mL) and diisopropylethylamine (0.82 mL, 4.73 mmol). The solution was cooled to 0° C. and ethoxycarbonyl isothiocyanate (0.21 mL, 1.73 mmol) was added dropwise. The mixture was allowed to warm to room temperature and was stirred 30 min. Methylene chloride (20 mL) was added, and the organic layer was washed with water (20 mL), 10% aqueous HCl (20 mL), and saturated brine (20 mL). The organic layer was dried with MgSO4, filtered and the solvent was removed in vacuo to yield the product as a yellow oil in 92% yield (502 mg, 1.45 mmol). 1H NMR (300 MHz, CDCl3): δ=10.10 (d, 1H, J=6.6 Hz), 8.11 (s, 1H), 7.27 (d, 2H, J=8.1 Hz), 7.10 (d, 2H, J=8.1 Hz), 5.25 (t, 1H, J=6.3 Hz), 4.23 (q, 2H, J=7.2 Hz), 3.73 (s, 3H), 3.32 (dd, 1H; J=14.1, 6.0 Hz), 3.20 (dd, 1H, J=13.8, 6.0 Hz), 1.30 (t, 3H, J=7.2 Hz); 13C NMR (75 mHz, CDCl3): δ=179.4, 170.8, 152.6, 134.2, 133.4, 130.8, 129.0, 63.2, 59.2, 53.6, 52.8, 36.8, 14.4; ESI-MS calcd for C14H17ClN2O4S [M+Na]+: 267.0495. found 267.0495. to warm to room temperature the organic layer was washed with water (20 mL), 10% aqueous HCl (20 mL), and saturated brine (20 mL) The organic layer was dried with MgSO4 filtered the solvent was removed in vacuo

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

Procedure: Methyl ester 1-1 (394 mg, 1.58 mmol) was dissolved in methylene chloride (4.0 mL) and diisopropylethylamine (0.82 mL, 4.73 mmol). The solution was cooled to 0° C. and ethoxycarbonyl isothiocyanate (0.21 mL, 1.73 mmol) was added dropwise. The mixture was allowed to warm to room temperature and was stirred 30 min. Methylene chloride (20 mL) was added, and the organic layer was washed with water (20 mL), 10% aqueous HCl (20 mL), and saturated brine (20 mL). The organic layer was dried with MgSO4, filtered and the solvent was removed in vacuo to yield the product as a yellow oil in 92% yield (502 mg, 1.45 mmol). 1H NMR (300 MHz, CDCl3): δ=10.10 (d, 1H, J=6.6 Hz), 8.11 (s, 1H), 7.27 (d, 2H, J=8.1 Hz), 7.10 (d, 2H, J=8.1 Hz), 5.25 (t, 1H, J=6.3 Hz), 4.23 (q, 2H, J=7.2 Hz), 3.73 (s, 3H), 3.32 (dd, 1H; J=14.1, 6.0 Hz), 3.20 (dd, 1H, J=13.8, 6.0 Hz), 1.30 (t, 3H, J=7.2 Hz); 13C NMR (75 mHz, CDCl3): δ=179.4, 170.8, 152.6, 134.2, 133.4, 130.8, 129.0, 63.2, 59.2, 53.6, 52.8, 36.8, 14.4; ESI-MS calcd for C14H17ClN2O4S [M+Na]+: 267.0495. found 267.0495. to warm to room temperature the organic layer was washed with water (20 mL), 10% aqueous HCl (20 mL), and saturated brine (20 mL) The organic layer was dried with MgSO4 filtered the solvent was removed in vacuo

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

Procedure: 4-Chloro-DL-phenylalanine (1.00 g, 5.00 mmol) was dissolved in methanol (30 mL) and cooled to 0° C. Thionyl chloride (2.92 mL, 40.0 mmol) was added dropwise. The mixture was allowed to warm to room temperature and was heated at reflux for 4 h. The solvent and reagents were removed in vacuo to yield the hydrochloride salt 1-1 as a white powder in quantitative yield (1.25 g, 5.00 mmol). 1H NMR (300 MHz, CD3OD): δ=7.37 (d, 2H, J=6.6 Hz), 7.27 (d, 2H, J=6.6 Hz), 4.34 (t, 1H, J=6.9 Hz), 3.81 (s, 3H), 3.26 (dd, 1H, J=14.4, 6.4 Hz), 3.18 (dd, 1H, J=14.4, 7.3 Hz); 13C NMR (75 mHz, CD3OD): δ=170.28, 134.87, 134.18, 132.11, 130.19, 54.99, 53.85, 38.81; ESI-MS calcd for C10H13ClNO2 [M+H]+: 214.0635. found 214.0638. to warm to room temperature was heated at reflux for 4 h The solvent and reagents were removed in vacuo

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

Procedure: 4-Chloro-DL-phenylalanine (1.00 g, 5.00 mmol) was dissolved in methanol (30 mL) and cooled to 0° C. Thionyl chloride (2.92 mL, 40.0 mmol) was added dropwise. The mixture was allowed to warm to room temperature and was heated at reflux for 4 h. The solvent and reagents were removed in vacuo to yield the hydrochloride salt 1-1 as a white powder in quantitative yield (1.25 g, 5.00 mmol). 1H NMR (300 MHz, CD3OD): δ=7.37 (d, 2H, J=6.6 Hz), 7.27 (d, 2H, J=6.6 Hz), 4.34 (t, 1H, J=6.9 Hz), 3.81 (s, 3H), 3.26 (dd, 1H, J=14.4, 6.4 Hz), 3.18 (dd, 1H, J=14.4, 7.3 Hz); 13C NMR (75 mHz, CD3OD): δ=170.28, 134.87, 134.18, 132.11, 130.19, 54.99, 53.85, 38.81; ESI-MS calcd for C10H13ClNO2 [M+H]+: 214.0635. found 214.0638. to warm to room temperature was heated at reflux for 4 h The solvent and reagents were removed in vacuo