Sodium Iodide → 3-Butenoicacid,2-[[(1,1-dimethylethoxy)carbonyl]amino]-(9CI)

HRID 488709Notes

Reaction equation

HRID 488709 reaction equation
[C:1]([O:5][C:6]([NH:8][CH:9]([CH:12]=[CH2:13])[CH2:10][OH:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].CC(C)=[O:16].OS(O)(=O)=O.O=[Cr](=O)=O.[Na+].[I-]>CC(C)=O>[C:1]([O:5][C:6]([NH:8][CH:9]([CH:12]=[CH2:13])[C:10]([OH:16])=[O:11])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 5238Sodium IodideHCID 13517889tert-Butyl (1-hydroxybut-3-en-2-yl)carbamateHCID 131709961Jones' reagent

Product 1

HCID 103527863-Butenoicacid,2-[[(1,1-dimethylethoxy)carbonyl]amino]-(9CI)

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

To a solution of 3 (50 mg, 0.267 mmol) in acetone (5 mL) was added Jones reagent (4 M, 0.2 mL, 0.8 mmol) at 0° C. over 10 min and the reaction mixture was then stirred for 3 h at rt. Excess Jones reagent was quenched by addition of i-PrOH. The acetone and i-PrOH were removed under reduced pressure, and the residue was partitioned between water and ethyl acetate. The organic phase was separated and the product was extracted into saturated aqueous Na2CO3 solution. Acidification of the aqueous phase to pH 4 with acetic acid followed by extraction with ethyl acetate, drying (MgSO4), filtration and evaporation gave Boc-protected vinylglycine (44 mg, 82%): 1H NMR (300 MHz, DMSO-d6) δ1.37 (s, 9H), 4.51 (dd, J=6, 7 Hz, 1H), 5.17 (d, J=10 Hz, 1H), 5.28 (d, J=17 Hz, 1H), 5.87 (ddd, J=6, 10, 17 Hz, 1H), 7.30 (d, J=7 Hz, 1H), 12.65 (br s, 1H); 13C NMR (75 MHZ, CDCl3) δ 28.2, 56.2, 78.2, 117.1, 133.1, 155.2, 172.0; HRMS (FAB, 3-NBA, NaI) calculated for C9H15NO4 Na (M+Na+) 224.0899, observed 224.0893.

Workup

  1. customExcess Jones reagent was quenched by addition of i-PrOH
  2. customThe acetone and i-PrOH were removed under reduced pressure
  3. customthe residue was partitioned between water and ethyl acetate
  4. customThe organic phase was separated
  5. extractionthe product was extracted into saturated aqueous Na2CO3 solution
  6. extractionAcidification of the aqueous phase to pH 4 with acetic acid followed by extraction with ethyl acetate
  7. customdrying
  8. filtration(MgSO4), filtration and evaporation
  9. customgave Boc-protected vinylglycine (44 mg, 82%)

Sources & evidence

ORD record
ord-2acfd29cf96f412e886b2805594c0fd8
Source dataset
uspto-grants-2005_12
Patent number
US06974665B2

Reaction notes

Loading…