Allylamine → Methyl 3-allylamino-2-benzyloxycarbonylamino-2-methylpropionate

HRID 1994431Notes

Reaction equation

HRID 1994431 reaction equation
[CH2:1]([NH2:4])[CH:2]=[CH2:3].[O-]S([O-])(=O)=O.[Mg+2].[CH2:11]([O:18][C:19]([NH:21][C:22]([CH3:29])([CH:27]=O)[C:23]([O:25][CH3:26])=[O:24])=[O:20])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1>C(Cl)Cl>[CH2:1]([NH:4][CH2:29][C:22]([NH:21][C:19]([O:18][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[O:20])([CH3:27])[C:23]([O:25][CH3:26])=[O:24])[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 7853AllylamineHCID 24083Sulfuric acid magnesium salt (1:1)HCID 85990941Methyl 2-benzyloxycarbonylamino-2-methyl-3-oxopropionate

Product 1

HCID 68691822Methyl 3-allylamino-2-benzyloxycarbonylamino-2-methylpropionateYield 102.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

1.237 ml (16.5 mmol) of allylamine and 0.9 g (7.48 mmol) of MgSO4 are added to a solution of 0.874 g (3.3 mmol) of methyl 2-benzyloxycarbonylamino-2-methyl-3-oxopropionate in 15 ml of DCM. The mixture is stirred at room temperature overnight. The reaction mixture was then filtered and concentrated in vacuo. 50 ml of anhydrous MeOH, 6 ml of NaCNBH3 (1.0M in THF) and 1.8 ml of acetic acid are added to the crude product. This mixture is stirred at RT for 2 h. The reaction solution is concentrated in vacuo, and then EtOAc and water are added. The organic phase is separated off and dried over MgSO4, and the solvent is removed in vacuo. Purification takes place by chromatography (25 g of SiO2, eluent MeOH/DCM (gradient 0-10%). 1.035 g of the desired product are obtained as an oil. MW=306 (calculated, monoisotopic), measured value: (M+H)+307.

Workup

  1. filtrationThe reaction mixture was then filtered
  2. concentrationconcentrated in vacuo
  3. addition50 ml of anhydrous MeOH, 6 ml of NaCNBH3 (1.0M in THF) and 1.8 ml of acetic acid are added to the crude product
  4. stirringThis mixture is stirred at RT for 2 h
  5. concentrationThe reaction solution is concentrated in vacuo
  6. additionEtOAc and water are added
  7. customThe organic phase is separated off
  8. dry with materialdried over MgSO4
  9. customthe solvent is removed in vacuo
  10. customPurification

Sources & evidence

ORD record
ord-88d126e1bfe84a958c22535094d5af53
Source dataset
uspto-grants-2010_01
Patent number
US07652007B2

Reaction notes

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