Water → Tert-butyl but-3-en-1-yl(2-oxo-3-(triphenylphosphoranylidene)propyl)carbamate

HRID 1754286Notes

Reaction equation

HRID 1754286 reaction equation
[CH2:1]([NH:5][C:6](=[O:12])[O:7][C:8]([CH3:11])([CH3:10])[CH3:9])[CH2:2][CH:3]=[CH2:4].[Li]CCCC.Cl[CH2:19][C:20](=[O:41])[CH:21]=[P:22]([C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.O>C1COCC1>[CH2:1]([N:5]([CH2:19][C:20](=[O:41])[CH:21]=[P:22]([C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)([C:23]1[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=1)[C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)[C:6](=[O:12])[O:7][C:8]([CH3:11])([CH3:10])[CH3:9])[CH2:2][CH:3]=[CH2:4]

Participants

6

Reactant 4

HCID 962WaterHCID 2870041-Chloro-3-(triphenyl phosphoranylidene)propan-2-oneHCID 11263760Tert-butyl but-3-EN-1-ylcarbamateHCID 178418339Butyllithium

Product 1

HCID 118222052Tert-butyl but-3-en-1-yl(2-oxo-3-(triphenylphosphoranylidene)propyl)carbamateYield 84%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-20 °C

Procedure

To a mixture of tert-butyl N-but-3-enylcarbamate (3.16 g, 18.42 mmol, 1.30 Eq) in THF (20 mL), was added n-BuLi (2.5 M, 14.74 mL, 2.60 Eq) at −78° C. under N2. The mixture was stirred at −20° C. for 1 hr. Then 1-chloro-3-(triphenyl phosphoranylidene)propan-2-one (5.00 g, 14.17 mmol, 1.00 Eq) in THF (20 mL) was added to the mixture at −78° C. under N2. The mixture was stirred at −20° C. for 3 hr. The resulting mixture was poured into water (30 mL) and stirred for 20 min. The aqueous phase was extracted with EA (10 mL). The combined organic phase was washed with saturated brine (20 mL*2), dried with anhydrous Na2SO4, filtered and concentrated in vacuum. The residue was purified by silica gel chromatography (PE/EA=1/1) to afford tert-butyl but-3-en-1-yl(2-oxo-3-(triphenylphosphoranylidene)propyl)carbamate (5.80 g, 11.90 mmol, 83.98% yield) as yellow solid.

Workup

  1. stirringThe mixture was stirred at −20° C. for 3 hr
  2. stirringstirred for 20 min
  3. extractionThe aqueous phase was extracted with EA (10 mL)
  4. washThe combined organic phase was washed with saturated brine (20 mL*2)
  5. dry with materialdried with anhydrous Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuum
  8. customThe residue was purified by silica gel chromatography (PE/EA=1/1)

Sources & evidence

ORD record
ord-7081b272b45c46479051cfa962e3ab54
Source dataset
uspto-grants-2015_10
Patent number
US09169212B2

Reaction notes

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