Allyl bromide → (S)-3-(Allyloxy)-2-((tert-butoxycarbonyl)amino)propanoic acid

HRID 1166453Notes

Reaction equation

HRID 1166453 reaction equation
[NH:1]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[C@H:2]([C:5]([OH:7])=[O:6])[CH2:3][OH:4].[H-].[Na+].[H][H].[CH2:19](Br)[CH:20]=[CH2:21]>CN(C=O)C>[NH:1]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[C@H:2]([C:5]([OH:7])=[O:6])[CH2:3][O:4][CH2:21][CH:20]=[CH2:19]

Participants

6

Reactant 4

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 98766N-[tert-butoxycarbonyl]-L-serineHCID 178418361HCID 178418361, compound

Product 1

HCID 11032134(S)-3-(Allyloxy)-2-((tert-butoxycarbonyl)amino)propanoic acidYield 79.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A solution of Boc-Ser-OH (1, 2.05 g, 10 mmol) in DMF (30 ml) is added to a stirred suspension of sodium hydride (60 wt % in mineral oil, 880 mg, 22 mmol) in DMF (30 ml) at 0° C. After the evolution of hydrogen gas ceased, allyl bromide (0.95 ml, 11 mmol) is added to the milk-colored solution. The resulting mixture is stirred at room temperature for 5 h to give a clear solution. The solvent is removed in vacuo, water (50 ml) is added, and the aqueous solution is extracted with ether (2×20 ml.) The aqueous solution is then acidified to pH 3.0 with 1.0 N HCl and extracted further with ethyl acetate (5×20 ml.) The combined ethyl acetate extracts are washed with water (20 ml), brine (20 ml), dried over anhydrous magnesium sulfate, and concentrated to give crude Boc-Ser(allyl)-OH (1.96 g) as a light yellow oil. A solution of this oil in ether (30 ml) is treated with dicyclohexylamine (1.594 ml, 8.0 mmol), the solvent removed, and the residue triturated with 1:9 ethyl acetate/hexane to yield 2 (2.26 g) as a colorless solid. An additional amount of 2 (0.58 g) is isolated from the trituration solution also as a colorless solid.

Workup

  1. customto give a clear solution
  2. customThe solvent is removed in vacuo, water (50 ml)
  3. additionis added
  4. extractionthe aqueous solution is extracted with ether (2×20 ml.) The aqueous solution
  5. extractionextracted further with ethyl acetate (5×20 ml.) The combined ethyl acetate extracts
  6. washare washed with water (20 ml), brine (20 ml)
  7. dry with materialdried over anhydrous magnesium sulfate
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-cd507ec4d9c7465e97b227a3856ad150
Source dataset
uspto-grants-2003_09
Patent number
US06613874B1

Reaction notes

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