2-Nitrobenzaldehyde → benzyl (S)-4-[2-(2-nitrobenzylamino)-1-propoxy]benzoate

HRID 354504Notes

Reaction equation

HRID 354504 reaction equation
[NH2:1][C@@H:2]([CH3:21])[CH2:3][O:4][C:5]1[CH:20]=[CH:19][C:8]([C:9]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[O:10])=[CH:7][CH:6]=1.[N+:22]([C:25]1[CH:32]=[CH:31][CH:30]=[CH:29][C:26]=1[CH:27]=O)([O-:24])=[O:23].[BH3-]C#N.[Na+]>CO.CC(O)=O>[N+:22]([C:25]1[CH:32]=[CH:31][CH:30]=[CH:29][C:26]=1[CH2:27][NH:1][C@@H:2]([CH3:21])[CH2:3][O:4][C:5]1[CH:20]=[CH:19][C:8]([C:9]([O:11][CH2:12][C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=2)=[O:10])=[CH:7][CH:6]=1)([O-:24])=[O:23]

Participants

5

Reactant 3

HCID 111012-NitrobenzaldehydeHCID 5003444Sodium cyanoborohydrideHCID 86587801benzyl (S)-4-(2-amino-1-propoxy)benzoate

Product 1

HCID 86587803benzyl (S)-4-[2-(2-nitrobenzylamino)-1-propoxy]benzoateYield 42.1%

Reagents, catalysts & solvents 1

HCID 10129899Acetic acid methanolSolvent

Procedure

To a stirred cooled (0° C.) solution of benzyl (S)-4-(2-amino-1-propoxy)benzoate (1.50 g, 5.26 mmol) and 2-nitrobenzaldehyde (0.87 g, 5.76 mmol) in MeOH—AcOH (16 mL, 15:1, v/v) was added NaBH3CN (1.65 g, 26.3 mmol), and the resulting mixture was stirred at room temp overnight. The mixture was quenched by sat. NaHCO3 and extracted with EtOAc. The extract was washed with brine, dried over Na2SO4, and evaporated. The residue was purified by column chromatography on silica-gel with CHCl3 to 5% MeOH in CHCl3 as eluent to give 931 mg (42%) benzyl (S)-4-[2-(2-nitrobenzylamino)-1-propoxy]benzoate as a yellow oil. 1H-NMR (CDCl3) δ1.21 (d, J=6.4 Hz, 3 H), 3.13-3.18 (m, 1 H), 3.88-3.97 (m 2 H), 4.06-4.20 (m, 2 H), 5.34 (s, 2 H), 6.89-6.94 (m, 2 H), 7.29-7.65 (m, 8 H), 7.94-8.03 (m, 3 H); MS (FAB) m/z 421 (M++1).

Workup

  1. customThe mixture was quenched by sat. NaHCO3
  2. extractionextracted with EtOAc
  3. washThe extract was washed with brine
  4. dry with materialdried over Na2SO4
  5. customevaporated
  6. customThe residue was purified by column chromatography on silica-gel with CHCl3 to 5% MeOH in CHCl3 as eluent

Sources & evidence

ORD record
ord-e696564ac47c48f59858c8e445d672ee
Source dataset
uspto-grants-2004_06
Patent number
US06756378B2

Reaction notes

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