Benzyl chloroformate → Ethyl 3-((benzyloxycarbonyl)(3-ethoxy-3-oxopropyl)amino)-4-(tert-butyldimethylsilyloxy)butanoate

HRID 1092797Notes

Reaction equation

HRID 1092797 reaction equation
[Si:1]([O:8][CH2:9][CH:10]([NH:17][CH2:18][CH2:19][C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C([O-])(O)=O.[Na+].Cl[C:31]([O:33][CH2:34][C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)=[O:32]>O1CCOCC1>[CH2:34]([O:33][C:31]([N:17]([CH2:18][CH2:19][C:20]([O:22][CH2:23][CH3:24])=[O:21])[CH:10]([CH2:9][O:8][Si:1]([C:4]([CH3:6])([CH3:7])[CH3:5])([CH3:3])[CH3:2])[CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])=[O:32])[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1

Participants

5

Reactant 3

HCID 10387Benzyl chloroformateHCID 516892Sodium BicarbonateHCID 86761499Ethyl 4-(tert-butyldimethylsilyloxy)-3-(3-ethoxy-3-oxopropylamino)butanoate

Product 1

HCID 66590022Ethyl 3-((benzyloxycarbonyl)(3-ethoxy-3-oxopropyl)amino)-4-(tert-butyldimethylsilyloxy)butanoateYield 73%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To the amine 3B (7.80 g, 21.6 mmol) and NaHCO3 (2.82 g, 33.6 mmol, 1.55 eq) in 40 mL anhydrous dioxane was added benzyl chloroformate (4.80 g, 28.1 mmol, 1.3 eq) at 0° C. over 5 mins. The ice bath was removed, and the mixture was allowed to warm to RT overnight. Solvents were removed in vacuo; the residue was diluted with 50 mL of water and 100 mL of EtOAc. The organic phase was separated, and the aqueous phase was further extracted with ethyl acetate (3×50 mL). The combined organic phase was dried over Na2SO4, and concentrated. The residue was chromatographed on SiO2 to afford 7.8 g (73%) of product 3C as a colorless liquid along with the recovery of 1.02 g starting material. ESI-MS:m/z 496.5 (M+H)+.

Workup

  1. customThe ice bath was removed
  2. customSolvents were removed in vacuo
  3. additionthe residue was diluted with 50 mL of water and 100 mL of EtOAc
  4. customThe organic phase was separated
  5. extractionthe aqueous phase was further extracted with ethyl acetate (3×50 mL)
  6. dry with materialThe combined organic phase was dried over Na2SO4
  7. concentrationconcentrated
  8. customThe residue was chromatographed on SiO2

Sources & evidence

ORD record
ord-b121c5a2215741aaafc50bbbbd650d4a
Source dataset
uspto-grants-2012_03
Patent number
US08129538B1

Reaction notes

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