(S)-(+)-2-(二苄氨基)-1-丙醇

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Dry DMSO (0.53 ml, 7.43 mmol) was added to a stirred solution of oxalyl chloride (0.31 ml, 3.6 mmol) in CH2Cl2 (7.5 ml) at −78° C. The solution was allowed to stir 15 minutes followed by the addition of 40 (740 mg, 2.90 mmol) in CH2Cl2 (7.5 ml). After 30 minutes, Et3N (1.0 ml, 7.2 mmol) was added and allowed to warm to room temperature. The solution was extracted with saturated. NaHCO3 (20 ml) and the aqueous layer was extracted with CH2Cl2 (2×15 ml). The organic layer was washed with saturated NaCl solution, dried with MgSO4 an concentrated in vacuo at room temperature to give 720 mg (98% yield) of a yellow oil which became a solid when cooled to −20° C. The aldehyde was used without further purification. mp 52-54° C., Literature mp 55.5° C. See, Dix et al., Arch Pharm (Weinheim) 1995, 328, 203-205.; [α]26D=−36.0 (c 1, CHCl3 Literature [α]20D=−35.1 (c 1, EtOAc); 1H NMR (400 MHz, CDCl3) δ1.19 (d, 2H, J=7.0 Hz), 3.34 (q, 1H, J=7.0 Hz), 3.58 (d, 2H, J=13.7 Hz), 3.74 (d, 2H, J=13.7 Hz), 7.26 (m, 2H), 7.33 (m, H), 7.42 (m, 4H), 9.74 (s, 1H); 13C NMR (100 MHz) δ6.7, 54.9, 62.8, 3.3, 4.4, 4.8, 139.1, 204.6; FABMS m/z 408.2 (M+MB), 254.2 (M+H), 22.2 (M-CHO); HRFABMS Calcd. for C17H20NO Mr 254.1545 (M+H). Found Mr 254.1545. After 30 minutes The solution was extracted with saturated NaHCO3 (20 ml) and the aqueous layer was extracted with CH2Cl2 (2×15 ml) The organic layer was washed with saturated NaCl solution dried with MgSO4 an concentrated in vacuo at room temperature

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a cold (−78° C.) solution of (COCl)2 (2M in CH2Cl2, 2.47 mL, 4.94 mmol) in CH2Cl2 (8 mL), DMSO (0.70 mL, 9.89 mmol) was added dropwise. After stirring at −78° C. for 15 min, a solution of (S)-2-(N,N-dibenzylamino)-1-propanol (1.01 g, 3.96 mmol) in CH2Cl2 (10 mL) was added dropwise. The mixture was stirred at −78° C. for 1 h, and then Et3N (2.76 mL, 19.78 mmol) was added. The reaction was warmed up to 0° C. and stirred for 15 min, followed by the addition of NH4Cl (25 mL, sat. aq.). The crude was extracted with CH2Cl2 (3×25 mL), washed successively with NaHCO3 (50 mL, sat. aq.) and brine (50 mL), dried over Na2SO4 and concentrated in vacuo. Aldehyde 4 was obtained as a yellow oil and used without further purification (928 mg, 93% yield). The mixture was stirred at −78° C. for 1 h The reaction was warmed up to 0° C. stirred for 15 min The crude was extracted with CH2Cl2 (3×25 mL) washed successively with NaHCO3 (50 mL, sat. aq.) and brine (50 mL) dried over Na2SO4 concentrated in vacuo

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Dry DMSO (0.53 mL, 7.43 mmol) was added to a stirred solution of oxalyl chloride (0.31 mL, 3.6 mmol) in CH2Cl2 (7.5 mL) at −78° C. The solution was allowed to stir 15 minutes followed by the addition of 40 (740 mg, 2.90 mmol) in CH2Cl2 (7.5 mL). After 30 minutes, Et3N (1.0 mL, 7.2 mmol) was added and allowed to warm to rt. The solution was extracted with satd. NaHCO3 (20 mL) and the aqueous layer was extracted with CH2Cl2 (2×15 mL). The organic layer was washed with satd. NaCl solution, dried with MgSO4 an concentrated in vacuo at rt to give 720 mg (98% yield) of a yellow oil which became a solid when cooled to −20° C. The aldehyde was used without further purification: mp 52-54° C. Lit. mp 55.5° C.; [α]26D=−36.0 (c 1,CHCl3 Lit. [α]20D=−35.1 (c 1, EtOAc); 1H NMR (400 MHz, CDCl3) δ 1.19 (d, 2H, J=7.0 Hz), 3.34 (q, 1H, J=7.0 Hz), 3.58 (d, 2H, J=13.7 Hz), 3.74 (d, 2H, J=13.7 Hz), 7.26 (m, 2H), 7.33 (m, H), 7.42 (m,4H), 9.74 (s, 1H); 13C NMR (100 MHz) δ 6.7, 54.9, 62.8, 3.3, 4.4, 4.8, 139.1, 204.6; FABMS m/z 408.2 (M+MB), 254.2 (M+H), 22.2 (M—CHO); HRFABMS calcd for C17H20NO Mr 254.1545 (M+H), found Mr254.1545. See, Dix et al., Arch Pharm (Weinheim) 1995, 328, 203-205. After 30 minutes The solution was extracted with satd NaHCO3 (20 mL) and the aqueous layer was extracted with CH2Cl2 (2×15 mL) The organic layer was washed with satd NaCl solution, dried with MgSO4 an concentrated in vacuo at rt

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Dry DMSO (0.53 mL, 7.43 mmol) was added to a stirred solution of oxalyl chloride (0.31 mL, 3.6 mmol) in CH2Cl2 (7.5 mL) at −78° C. The solution was allowed to stir 15 minutes followed by the addition of 40 (740 mg, 2.90 mmol) in CH2Cl2 (7.5 mL). After 30 minutes, Et3N (1.0 mL, 7.2 mmol) was added and allowed to warm to rt. The solution was extracted with satd. NaHCO3 (20 mL) and the aqueous layer was extracted with CH2Cl2 (2×15 mL). The organic layer was washed with satd. NaCl solution, dried with MgSO4 an concentrated in vacuo at rt to give 720 mg (98% yield) of a yellow oil which became a solid when cooled to −20° C. The aldehyde was used without further purification: mp 52-54° C. Lit. mp 55.5° C.; [α]26D=−36.0 (c 1,CHCl3 Lit. [α]20D=−35.1 (c 1, EtOAc); 1H NMR (400 MHz, CDCl3) δ 1.19 (d, 2H, J=7.0 Hz), 3.34 (q, 1H, J=7.0 Hz), 3.58 (d, 2H, J=13.7 Hz), 3.74 (d, 2H, J=13.7 Hz), 7.26 (m, 2H), 7.33 (m, H), 7.42 (m,4H), 9.74 (s, 1H); 13C NMR (100 MHz) δ 6.7, 54.9, 62.8, 3.3, 4.4, 4.8, 139.1, 204.6; FABMS m/z 408.2 (M+MB), 254.2 (M+H), 22.2 (M—CHO); HRFABMS calcd for C17H20NO Mr 254.1545 (M+H), found Mr254.1545. See, Dix et al., Arch Pharm (Weinheim) 1995, 328, 203-205. After 30 minutes The solution was extracted with satd NaHCO3 (20 mL) and the aqueous layer was extracted with CH2Cl2 (2×15 mL) The organic layer was washed with satd NaCl solution, dried with MgSO4 an concentrated in vacuo at rt

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a stirred suspension of phtalimide (824 mg, 5.60 mmol), (S)-2-(dibenzylamino)propan-1-ol (1.02 g, 4.00 mmol) and PPh3 (1.47 g, 5.60 mmol) in THF (30 mL) cooled to 0° C. under N2 was added dropwise DEAD (1.2 mL, 7.60 mmol). The resulting mixture was allowed to warm to room temperature and stirred overnight. The solvent was evaporated. The residue was purified by flash chromatography (silica gel, cyclohexane/methylene chloride 5/5) to afford a white solid (1.08 g, 70%). to warm to room temperature The solvent was evaporated The residue was purified by flash chromatography (silica gel, cyclohexane/methylene chloride 5/5)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Dry DMSO (0.53 ml, 7.43 mmol) was added to a stirred solution of oxalyl chloride (0.31 ml, 3.6 mmol) in CH2Cl2 (7.5 ml) at −78° C. The solution was allowed to stir 15 minutes followed by the addition of 40 (740 mg, 2.90 mmol) in CH2Cl2 (7.5 ml). After 30 minutes, Et3N (1.0 ml, 7.2 mmol) was added and allowed to warm to room temperature. The solution was extracted with saturated. NaHCO3 (20 ml) and the aqueous layer was extracted with CH2Cl2 (2×15 ml). The organic layer was washed with saturated NaCl solution, dried with MgSO4 an concentrated in vacuo at room temperature to give 720 mg (98% yield) of a yellow oil which became a solid when cooled to −20° C. The aldehyde was used without further purification. mp 52-54° C., Literature mp 55.5° C. See, Dix et al., Arch Pharm (Weinheim) 1995, 328, 203-205.; [α]26D=−36.0 (c 1, CHCl3 Literature [α]20D=−35.1 (c 1, EtOAc); 1H NMR (400 MHz, CDCl3) δ1.19 (d, 2H, J=7.0 Hz), 3.34 (q, 1H, J=7.0 Hz), 3.58 (d, 2H, J=13.7 Hz), 3.74 (d, 2H, J=13.7 Hz), 7.26 (m, 2H), 7.33 (m, H), 7.42 (m, 4H), 9.74 (s, 1H); 13C NMR (100 MHz) δ6.7, 54.9, 62.8, 3.3, 4.4, 4.8, 139.1, 204.6; FABMS m/z 408.2 (M+MB), 254.2 (M+H), 22.2 (M-CHO); HRFABMS Calcd. for C17H20NO Mr 254.1545 (M+H). Found Mr 254.1545. After 30 minutes The solution was extracted with saturated NaHCO3 (20 ml) and the aqueous layer was extracted with CH2Cl2 (2×15 ml) The organic layer was washed with saturated NaCl solution dried with MgSO4 an concentrated in vacuo at room temperature

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Dry DMSO (0.53 ml, 7.43 mmol) was added to a stirred solution of oxalyl chloride (0.31 ml, 3.6 mmol) in CH2Cl2 (7.5 ml) at −78° C. The solution was allowed to stir 15 minutes followed by the addition of 40 (740 mg, 2.90 mmol) in CH2Cl2 (7.5 ml). After 30 minutes, Et3N (1.0 ml, 7.2 mmol) was added and allowed to warm to room temperature. The solution was extracted with saturated. NaHCO3 (20 ml) and the aqueous layer was extracted with CH2Cl2 (2×15 ml). The organic layer was washed with saturated. NaCl solution, dried with MgSO4 an concentrated in vacuo at room temperature to give 720 mg (98% yield) of a yellow oil which became a solid when cooled to −20° C. The aldehyde was used without further purification: mp 52–54° C., Literature mp 55.5° C. See, Dix et al., Arch Pharm (Weinheim) 1995, 328, 203–205.; [α]26D=−36.0 (c 1, CHCl3) Literature [α]20D=−35.1 (c 1, EtOAc); 1H NMR (400 MHz, CDCl3) d 1.19 (d, 2H, J=7.0 Hz), 3.34 (q, 1H, J=7.0 Hz), 3.58 (δ, 2H, J=13.7 Hz), 3.74 (d, 2H, J=13.7 Hz), 7.26 (m, 2H), 7.33 (m, H), 7.42 (m, 4H), 9.74 (s, 1H); 13C NMR (100 MHz) δ 6.7, 54.9, 62.8, 3.3, 4.4, 4.8, 139.1, 204.6; FABMS m/z 408.2 (M+MB), 254.2 (M+H), 22.2 (M-CHO); HRFABMS calcd for C17H20NO Mr 254.1545 (M+H), found Mr 254.1545. After 30 minutes The solution was extracted with saturated NaHCO3 (20 ml) and the aqueous layer was extracted with CH2Cl2 (2×15 ml) The organic layer was washed with saturated NaCl solution, dried with MgSO4 an concentrated in vacuo at room temperature

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Dry DMSO (0.53 ml, 7.43 mmol) was added to a stirred solution of oxalyl chloride (0.31 ml, 3.6 mmol) in CH2Cl2 (7.5 ml) at −78° C. The solution was allowed to stir 15 minutes followed by the addition of 40 (740 mg, 2.90 mmol) in CH2Cl2 (7.5 ml). After 30 minutes, Et3N (1.0 ml, 7.2 mmol) was added and allowed to warm to room temperature. The solution was extracted with saturated. NaHCO3 (20 ml) and the aqueous layer was extracted with CH2Cl2 (2×15 ml). The organic layer was washed with saturated. NaCl solution, dried with MgSO4 an concentrated in vacuo at room temperature to give 720 mg (98% yield) of a yellow oil which became a solid when cooled to −20° C. The aldehyde was used without further purification: mp 52–54° C., Literature mp 55.5° C. See, Dix et al., Arch Pharm (Weinheim) 1995, 328, 203–205.; [α]26D=−36.0 (c 1, CHCl3) Literature [α]20D=−35.1 (c 1, EtOAc); 1H NMR (400 MHz, CDCl3) d 1.19 (d, 2H, J=7.0 Hz), 3.34 (q, 1H, J=7.0 Hz), 3.58 (δ, 2H, J=13.7 Hz), 3.74 (d, 2H, J=13.7 Hz), 7.26 (m, 2H), 7.33 (m, H), 7.42 (m, 4H), 9.74 (s, 1H); 13C NMR (100 MHz) δ 6.7, 54.9, 62.8, 3.3, 4.4, 4.8, 139.1, 204.6; FABMS m/z 408.2 (M+MB), 254.2 (M+H), 22.2 (M-CHO); HRFABMS calcd for C17H20NO Mr 254.1545 (M+H), found Mr 254.1545. After 30 minutes The solution was extracted with saturated NaHCO3 (20 ml) and the aqueous layer was extracted with CH2Cl2 (2×15 ml) The organic layer was washed with saturated NaCl solution, dried with MgSO4 an concentrated in vacuo at room temperature

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Dry DMSO (0.53 mL, 7.43 mmol) was added to a stirred solution of oxalyl chloride (0.31 mL, 3.6 mmol) in CH2Cl2 (7.5 mL) at -78° C. The solution was allowed to stir 15 minutes followed by the addition of 40 (740 mg, 2.90 mmol) in CH2Cl2 (7.5 mL). After 30 minutes, Et3N (1.0 mL, 7.2 mmol) was added and allowed to warm to rt. The solution was extracted with satd. NaHCO3 (20 mL) and the aqueous layer was extracted with CH2Cl2 (2×15 mL). The organic layer was washed with satd. NaCl solution, dried with MgSO4 an concentrated in vacuo at rt to give 720 mg (98% yield) of a yellow oil which became a solid when cooled to -20° C. The aldehyde was used without further purification: mp 52-54° C. Lit. mp 55.5° C.; [α]26D =-36.0 (c 1,CHCl3Lit. [α]20D =-35.1 (c 1, EtOAc); 1H NMR (400 MHz, CDCl3) δ 1.19 (d, 2H, J=7.0 Hz), 3.34 (q, 1H, J=7.0 Hz), 3.58 (d, 2H, J=13.7 Hz), 3.74 (d, 2H, J=13.7 Hz), 7.26 (m, 2H), 7.33 (m, H), 7.42 (m,4H), 9.74 (s, 1H); 13C NMR (100 MHz) δ 6.7, 54.9, 62.8, 3.3, 4.4, 4.8, 139.1, 204.6; FABMS m/z 408.2 (M+MB), 254.2 (M+H), 22.2 (M--CHO); HRFABMS calcd for C17H20NO Mr 254.1545 (M+H), found Mr 254.1545. See, Dix et al., Arch Pharm (Weinheim) 1995, 328, 203-205. After 30 minutes The solution was extracted with satd NaHCO3 (20 mL) and the aqueous layer was extracted with CH2Cl2 (2×15 mL) The organic layer was washed with satd NaCl solution, dried with MgSO4 an concentrated in vacuo at rt

反应条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a cold (−78° C.) solution of (COCl)2 (2M in CH2Cl2, 2.47 mL, 4.94 mmol) in CH2Cl2 (8 mL), DMSO (0.70 mL, 9.89 mmol) was added dropwise. After stirring at −78° C. for 15 min, a solution of (S)-2-(N,N-dibenzylamino)-1-propanol (1.01 g, 3.96 mmol) in CH2Cl2 (10 mL) was added dropwise. The mixture was stirred at −78° C. for 1 h, and then Et3N (2.76 mL, 19.78 mmol) was added. The reaction was warmed up to 0° C. and stirred for 15 min, followed by the addition of NH4Cl (25 mL, sat. aq.). The crude was extracted with CH2Cl2 (3×25 mL), washed successively with NaHCO3 (50 mL, sat. aq.) and brine (50 mL), dried over Na2SO4 and concentrated in vacuo. Aldehyde 4 was obtained as a yellow oil and used without further purification (928 mg, 93% yield). The mixture was stirred at −78° C. for 1 h The reaction was warmed up to 0° C. stirred for 15 min The crude was extracted with CH2Cl2 (3×25 mL) washed successively with NaHCO3 (50 mL, sat. aq.) and brine (50 mL) dried over Na2SO4 concentrated in vacuo

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Dry DMSO (0.53 mL, 7.43 mmol) was added to a stirred solution of oxalyl chloride (0.31 mL, 3.6 mmol) in CH2Cl2 (7.5 mL) at −78° C. The solution was allowed to stir 15 minutes followed by the addition of 40 (740 mg, 2.90 mmol) in CH2Cl2 (7.5 mL). After 30 minutes, Et3N (1.0 mL, 7.2 mmol) was added and allowed to warm to rt. The solution was extracted with satd. NaHCO3 (20 mL) and the aqueous layer was extracted with CH2Cl2 (2×15 mL). The organic layer was washed with satd. NaCl solution, dried with MgSO4 an concentrated in vacuo at rt to give 720 mg (98% yield) of a yellow oil which became a solid when cooled to −20° C. The aldehyde was used without further purification: mp 52-54° C. Lit. mp 55.5° C.; [α]26D=−36.0 (c 1,CHCl3 Lit. [α]20D=−35.1 (c 1, EtOAc); 1H NMR (400 MHz, CDCl3) δ 1.19 (d, 2H, J=7.0 Hz), 3.34 (q, 1H, J=7.0 Hz), 3.58 (d, 2H, J=13.7 Hz), 3.74 (d, 2H, J=13.7 Hz), 7.26 (m, 2H), 7.33 (m, H), 7.42 (m,4H), 9.74 (s, 1H); 13C NMR (100 MHz) δ 6.7, 54.9, 62.8, 3.3, 4.4, 4.8, 139.1, 204.6; FABMS m/z 408.2 (M+MB), 254.2 (M+H), 22.2 (M—CHO); HRFABMS calcd for C17H20NO Mr 254.1545 (M+H), found Mr254.1545. See, Dix et al., Arch Pharm (Weinheim) 1995, 328, 203-205. After 30 minutes The solution was extracted with satd NaHCO3 (20 mL) and the aqueous layer was extracted with CH2Cl2 (2×15 mL) The organic layer was washed with satd NaCl solution, dried with MgSO4 an concentrated in vacuo at rt

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a stirred suspension of phtalimide (824 mg, 5.60 mmol), (S)-2-(dibenzylamino)propan-1-ol (1.02 g, 4.00 mmol) and PPh3 (1.47 g, 5.60 mmol) in THF (30 mL) cooled to 0° C. under N2 was added dropwise DEAD (1.2 mL, 7.60 mmol). The resulting mixture was allowed to warm to room temperature and stirred overnight. The solvent was evaporated. The residue was purified by flash chromatography (silica gel, cyclohexane/methylene chloride 5/5) to afford a white solid (1.08 g, 70%). to warm to room temperature The solvent was evaporated The residue was purified by flash chromatography (silica gel, cyclohexane/methylene chloride 5/5)