Allyl bromide → HCID 85970119, compound

HRID 2215214Notes

Reaction equation

HRID 2215214 reaction equation
[CH2:1]([O:3][C:4](=[O:13])[CH2:5][NH:6][C:7](=[O:12])[C:8]([CH3:11])([CH3:10])[CH3:9])[CH3:2].C[Si](C)(C)[N-][Si](C)(C)C.[Li+].[CH2:24](Br)[CH:25]=[CH2:26]>C1COCC1>[CH2:1]([O:3][C:4](=[O:13])[CH:5]([NH:6][C:7](=[O:12])[C:8]([CH3:9])([CH3:11])[CH3:10])[CH2:26][CH:25]=[CH2:24])[CH3:2]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 2733832Lithium HexamethyldisilazideHCID 3622015HCID 3622015, compound

Product 1

HCID 85970119HCID 85970119, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

13.06 g of the above prepared (2,2-dimethyl-propionylamino)-acetic acid ethyl ester (69.75 mmol) was dissolved in 350 ml of abs. THF and cooled down to −78°. 146 ml of 1M lithium hexamethyldisilazide in THF (2.1 eq.) were slowly added via dropping funnel. After keeping the yellow suspension for 30 Min. at −78°, 6.491 ml of allyl bromide (1.1 eq.) was added and stirring continued for 15 Min. at the same temperature and for 40 Min. at 0°. Pouring of the homogeneous reaction mixture onto crashed ice/HCl, twofold extraction with AcOEt, twofold washing with water, drying over sodium sulfate, and evaporation of the solvents, followed by flash chromatography (SiO2, hexane/AcOEt=8/2) afforded 10.50 g of the title compound as colorless solid. In addition, 2.70 g of the di-allylated product (2-allyl-2-(2,2-dimethyl-propionylamino)-pent-4-enoic acid ethyl ester) was obtained from the less polar fractions.

Workup

  1. dissolutionwas dissolved in 350 ml of abs
  2. customat 0°
  3. additionPouring of the homogeneous reaction mixture
  4. extractionice/HCl, twofold extraction with AcOEt
  5. washtwofold washing with water
  6. dry with materialdrying over sodium sulfate, and evaporation of the solvents

Sources & evidence

ORD record
ord-20491c2beab74915a514d48324e71bf4
Source dataset
uspto-grants-2006_09
Patent number
US07109225B2

Reaction notes

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