Ammonium Chloride → 2-Benzyloxycarbonylamino-1-phenyl-3-butene

HRID 2182494Notes

Reaction equation

HRID 2182494 reaction equation
[CH2:1]([Li])CCC.[C:6]([NH:16][C@H:17]([CH:25]=O)[CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)([O:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)=[O:7].[NH4+].[Cl-]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCCC1>[CH2:9]([O:8][C:6]([NH:16][CH:17]([CH:25]=[CH2:1])[CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:7])[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1

Participants

6

Reactant 3

HCID 25517Ammonium ChlorideHCID 7021150Cbz-L-PhenylalaninalHCID 178418339Butyllithium

Product 1

HCID 136065862-Benzyloxycarbonylamino-1-phenyl-3-butene

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred suspension of methyltriphenylphosphonium bromide (10.72 g, 0.03 moles) in 100 mL of dry tetrahydofuran at −78° C. was added dropwise 1.6M n-butyl lithium (17.5 mL, 0.028 moles), and the mixture was stirred for 0.5 hrs at −78˜−20° C. Then was added a solution of N-Cbz-phenylalaninal (5.67 g, 0.02 moles) in 50 mL of dry tetrahydrofuran, and the mixture was stirred for 16 hrs at room temperature. After addition of saturated NH4Cl (50 mL) the mixture was extracted with EtOAc, and the extract was washed with water and brine. It was dried over Na2SO4 and evaporated to give an oily residue. The crude product was purified by column chromatograpy on silica gel with elution by 5:95. EtOAc-hexane to give pure 2-benzyloxycarbonylamino-1-phenyl-3-butene. Part B: Preparation of 2-benzyloxycarbonylamino-1-phenyl-3,4-epoxy-butane.

Workup

  1. stirringthe mixture was stirred for 16 hrs at room temperature
  2. extractionwas extracted with EtOAc
  3. washthe extract was washed with water and brine
  4. dry with materialIt was dried over Na2SO4
  5. customevaporated
  6. customto give an oily residue
  7. customThe crude product was purified by column chromatograpy on silica gel with elution by 5:95

Sources & evidence

ORD record
ord-dbb76d37dfa54c22b363803f0fa67167
Source dataset
uspto-grants-2005_05
Patent number
US06897234B2

Reaction notes

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