Sodium Bicarbonate → 5-Azido-N-Boc-L-Norvaline

HRID 1482360Notes

Reaction equation

HRID 1482360 reaction equation
C(=O)(O)[O-].[Na+].[NH:6]([C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[C@H:7]([C:12]([OH:14])=[O:13])[CH2:8][CH2:9][CH2:10][NH2:11].Cl.N1(S([N:31]=[N+:32]=[N-])(=O)=O)C=CN=C1.S(=O)(=O)(O)[O-].[K+]>CO.O.O.O.O.O.S([O-])([O-])(=O)=O.[Cu+2].O>[N:11]([CH2:10][CH2:9][CH2:8][C@H:7]([NH:6][C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16])[C:12]([OH:14])=[O:13])=[N+:31]=[N-:32]

Participants

8

Reactant 4

HCID 516892Sodium BicarbonateHCID 516920Potassium bisulfateHCID 7018784(2S)-5-amino-2-{[(tert-butoxy)carbonyl]amino}pentanoic acidHCID 235839821H-Imidazole-1-sulfonyl azide hydrochloride

Product 1

HCID 236291975-Azido-N-Boc-L-Norvaline

Reagents, catalysts & solvents 3

HCID 24463Copper sulfate pentahydrateCatalystHCID 887MethanolSolventHCID 962WaterSolvent

Procedure

Sodium bicarbonate (1.99 g, 23.68 mmol) was added to a mixture of Boc-Orn-OH (Compound tk56) (1.0 g, 4.31 mmol) and copper sulfate pentahydrate (21 mg, 0.086 mmol) in methanol (20 mL)-water (6 mL) at room temperature, followed by addition of 1H-imidazole-1-sulfonyl azide hydrochloride synthesized by the method described in the literature (Org. Lett., 2007, 9, 3797) (1.08 g, 5.17 mmol). The reaction mixture was stirred at room temperature for 24 hours. The reaction mixture was cooled in an ice bath, followed by addition of a saturated aqueous potassium bisulfate solution (8 mL). The resulting mixture was extracted with ethyl acetate (three times), and the organic phase was concentrated under reduced pressure. The resulting residue was purified by reverse-phase silica gel column chromatography (0.05% aqueous trifluoroacetic acid solution/0.05% trifluoroacetic acid-acetonitrile solution) to afford (S)-5-azido-2-((tert-butoxycarbonyl)amino)pentanoic acid (Compound tk69) (1.19 g, quant.).

Workup

  1. customsynthesized by the method
  2. temperatureThe reaction mixture was cooled in an ice bath
  3. extractionThe resulting mixture was extracted with ethyl acetate (three times)
  4. concentrationthe organic phase was concentrated under reduced pressure
  5. customThe resulting residue was purified by reverse-phase silica gel column chromatography (0.05% aqueous trifluoroacetic acid solution/0.05% trifluoroacetic acid-acetonitrile solution)

Sources & evidence

ORD record
ord-4734c4b818814529aa0b34210d474512
Source dataset
uspto-grants-2016_08
Patent number
US09409952B2

Reaction notes

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