L-Aspartic Acid → 2-Allyloxycarbonylamino-succinic acid 4-tert-butyl ester

HRID 1824431Notes

Reaction equation

HRID 1824431 reaction equation
[NH2:1][C@H:2]([C:7]([OH:9])=[O:8])[CH2:3][C:4]([OH:6])=[O:5].Cl[C:11]([O:13][CH2:14][CH:15]=[CH2:16])=[O:12].[C:17](=O)(O)[O-].[Na+].[CH2:22]1[CH2:26]OC[CH2:23]1>O>[C:22]([O:5][C:4](=[O:6])[CH2:3][CH:2]([NH:1][C:11]([O:13][CH2:14][CH:15]=[CH2:16])=[O:12])[C:7]([OH:9])=[O:8])([CH3:23])([CH3:26])[CH3:17]

Participants

6

Reactant 4

HCID 5960L-Aspartic AcidHCID 8028TetrahydrofuranHCID 18052Allyl chloroformateHCID 516892Sodium Bicarbonate

Product 1

HCID 235986592-Allyloxycarbonylamino-succinic acid 4-tert-butyl esterYield 90%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

L-aspartic acid □-t-butyl ester (30.3 g, 0.160 mol) is dissolved in 100 mL THF and 300 mL H2O. Under cooling (ice bath) and with stirring, allyl chloroformate (38.8 mL, 44.1 g, 0.365 mol) and sodium bicarbonate (60.1 g, 0.715 mol) are added in one portion. After the consumption of the starting material, the mixture is acidified to a pH of 2 using 6 N HCl and then extracted with ether (3×400 mL). The ether layer is dried with MgSO4 and concentrated under reduced pressure. The residue is purified over silica (CH2Cl2/MeOH/acetic acid 3:97:0.1) to furnish 40.7 g (90% yield) of the desired product as a clear oil. 1H-NMR (300 MHz, CDCl3): δ 1.46 (s, 9H), 2.76–3.03 (ABX, J=59.3, 17.2, 4.4, 2H), 4.60–4.66 (br m, 3H), 5.30 (m, 2H), 5.82–5.84 (d, J=8.4), 5.87–6.00 (m, 1H), 10.94 (br s, 1H); MS (ESI): m/e=274.08 (M+H).

Workup

  1. temperatureUnder cooling (ice bath)
  2. customAfter the consumption of the starting material
  3. extractionextracted with ether (3×400 mL)
  4. dry with materialThe ether layer is dried with MgSO4
  5. concentrationconcentrated under reduced pressure
  6. customThe residue is purified over silica (CH2Cl2/MeOH/acetic acid 3:97:0.1)

Sources & evidence

ORD record
ord-6ae408d001614b8eb08e11a3bed97d54
Source dataset
uspto-grants-2006_05
Patent number
US07041696B2

Reaction notes

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