Acetic Acid → HCID 86747603, compound

HRID 1975486Notes

Reaction equation

HRID 1975486 reaction equation
C(OC([NH:7][CH2:8][CH:9]([C:18]1[CH2:24][C@H:23]2[N:20]([C:21](=[O:28])[C@@H:22]2[C@H](O)C)[C:19]=1[C:29]([O:31]CC=C)=[O:30])[CH2:10][NH:11][C:12](OCC=C)=O)=O)C=C.[C:35]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C[CH:36]=1.[C:54]([OH:57])(=[O:56])[CH3:55].C([SnH](CCCC)CCCC)CCC>O1CCCC1.C(O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(OCC)(=O)C>[CH2:35]([O:56][C:54]([CH2:55][C:12]1[NH:11][CH2:10][CH:9]([C:18]2[CH2:24][CH:23]3[N:20]([C:21](=[O:28])[CH2:22]3)[C:19]=2[C:29]([OH:31])=[O:30])[CH2:8][N:7]=1)=[O:57])[CH3:36]

Participants

9

Reactant 4

HCID 176Acetic AcidHCID 5948TributylstannaneHCID 11776TriphenylphosphineHCID 57160014HCID 57160014, compound

Product 1

HCID 86747603HCID 86747603, compound

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
30 °C

Procedure

To a solution of allyl (5R,6S)-3-[2-allyloxycarbonylamino-1-(N-allyloxycarbonylaminomethyl)ethyl]-6-[(1R)-1-hydroxyethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate (858 mg) in tetrahydrofuran (12 ml) and ethanol (4 ml) were added successively triphenylphosphine (0.19 g), acetic acid (0.10 ml) and tetrakis(triphenylphosphine)palladium (0.16 g) at room temperature under nitrogen. The temperature was raised to 30° C. and after all components were dissolved, tributyltin hydride (1.94 ml) was added dropwise. After stirring for 15 minutes at room temperature, ethyl acetate (50 ml) was added. After 30 minutes, the precipitate was filtrated and washed with ethyl acetate and dichloromethane under nitrogen, and dissolved in buffer solution (68 ml, pH 6.86). Ethyl 2-ethoxycarbonylacetoimidate hydrochloride (599 mg) was added to the solution at pH 8.5. After stirring for 30 minutes at pH 8.5. The mixture was stirred for 30 minutes at pH 7. After the starting material disappeared, the reaction mixture was washed five times with ethyl acetate-tetrahydrofuran (7:3, V/V, 70 ml) at pH 7. The aqueous layer was evaporated and the residue was purified by Diaion HP-20 column chromatography (eluent:acetonitrile-water=4:96, V/V) and silica gel column chlomatorgaphy (eluent:acetonitrile-water=100:00-85:15, V/V) to give (5R,6S)-6-[1R)-1-hydroxyethyl]-3-[2-(ethoxycarbonylmethyl)-3,4,5,6-tetrahydropyrimidin-5-yl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylic acid (56.4 mg).

Workup

  1. dissolutionafter all components were dissolved
  2. waitAfter 30 minutes
  3. filtrationthe precipitate was filtrated
  4. washwashed with ethyl acetate and dichloromethane under nitrogen
  5. dissolutiondissolved in buffer solution (68 ml, pH 6.86)
  6. additionEthyl 2-ethoxycarbonylacetoimidate hydrochloride (599 mg) was added to the solution at pH 8.5
  7. stirringAfter stirring for 30 minutes at pH 8.5
  8. stirringThe mixture was stirred for 30 minutes at pH 7
  9. washthe reaction mixture was washed five times with ethyl acetate-tetrahydrofuran (7:3, V/V, 70 ml) at pH 7
  10. customThe aqueous layer was evaporated
  11. customthe residue was purified by Diaion HP-20 column chromatography (eluent:acetonitrile-water=4:96, V/V) and silica gel column chlomatorgaphy (eluent:acetonitrile-water=100:00-85:15, V/V)

Sources & evidence

ORD record
ord-e85b24efbf1e4e299701439aa9a79339
Source dataset
uspto-grants-1994_02
Patent number
US05286721

Reaction notes

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